Polyarylene and method for production thereof

ABSTRACT

This invention provides polyarylenes having a recurring unit shown by formula (I) or (II) below and a process for production thereof as well as these monomers: (wherein Ar 1  and Ar 2  are an arylene; R 1  and R 2  are C 1 -C 20  hydrocarbon group, etc.; A 1  and A 2  are C 1 -C 20  hydrocarbon group, etc.; and n is an integer of 2 or more);                    
     (wherein Ar 1  and Ar 2  are an arylene; R 1  and R 2  are C 1 -C 20  hydrocarbon group, etc.; A 1  and A 2  are C 1 -C 20  hydrocarbon group, etc.; and n is an integer of 2 or more) The polyarylenes of the invention find extensive applications as electrically conductive resins. The polyarylenes can be used also as resin compositions in a variety of formed shapes.

FIELD OF THE INVENTION

The present invention relates to a polyarylene, a teraryl and a terarylprecursor, as well as to a method for producing a polyarylene. Moreparticularly, the invention relates to a polyarylene having terarylenerecurring units on the backbone and a method for production thereof.

BACKGROUND ART

Polyarylenes are of interest because the arylene group as a recurringunit has excellent thermal and chemical stability. Also, polyaryleneshave been attracting considerable attention to their peculiar physicalproperties because of the advanced π-electron conjugated system.

A variety of applications as, e.g., conductive polymers are anticipatedfor polyarylenes. Polyphenylene s may also be either oxidized or reducedso that anions or cations are doped to form p type or n typesemiconductors. Utilizing the property, it is also expected to applypoly(p-phenylene) to electrode materials or apply as display elementsusing a change in absorbance upon oxidation or reduction.

Moreover, polyarylenes are expected to be applicable to macro moleculelight emitting elements. In this field, elements called macro moleculelight emitting electrochemical elements (LEC) have been proposed latelyand drawn attention in view of their high luminous efficiency. Thestructure includes two electrodes, between which a electricallyconductive polymer material and a polymer membrane comprisingpolyethylene oxide having ionic conductivity and a substrate salt areinserted. It is assumed that the principle of working mechanism is basedon the input of positive and negative charges from the electrodes andthe transfer of both positive and negative ions of the substrate salt asa dopant, whereby a p-n junction would be formed in the membrane. If anionic conductivity is further imparted to conductive polymer substanceshaving an electronic conductivity, such light emitting elements will bemanufactured using a sole material, not with the composite membranementioned above, resulting in a great advantage in manufacturing steps.

Processes for manufacturing polyarylenes such as polyphenylene have beenhitherto limited. For manufacturing polyphenylenes, for example,oxidative cation polymerization called the Kovacic process, which ispolycondensation using benzene as a monomer, is known. As is describedin P. Kovacic, et al., Chem. Rev., 1987, 87, 357-379, an oxidizing agentsuch as cupric chloride and a Lewis acid catalyst such as aluminumchloride are employed to form insoluble polyphenylene of uncertainstructure. It is reported that polyphenylene formed by oxidation ofbenzene is branched polyphenylene with a low molecular weight.

Further processes are proposed for manufacturing polyarylenes, whichinclude electrochemical oxidative polymerization (a process using acupric chloride-lithium aluminum hexafluoride-based electrolyte andapplying a voltage between electrodes to produce a polymer on theelectrodes); as polycondensation of substituted benzene derivatives,Wurtz-Fittig reaction (a process involving condensation of adihalogenobenzene with an alkali metal) Ullmann reaction (a processinvolving condensation of diiodobenzene with a metal copper), Grignardreaction called Yamamoto method (a process involving condensation of adihalogenobenzene Grignard derivative with a nickel chloride-bipyridylcomplex), diazonium coupling (a process involving condensation of adiazonium derivative with sodium nitrite/hydrochloric acid followed bytreatment with copper chloride); as processes via precursors,dehydration of cyclohexadiene polymer, a bio-engineering method (whichcomprises oxidizing benzene with bacteria to synthesize5,6-dihydroxycyclohexane-1,3-diene, subjecting the carbonic acid esterof the diene to radical polymerization and then heating the resultingintermediate polymer to effect synthesis); and so on.

DISCLOSURE OF THE INVENTION

However, polyarylenes having terarylene recurring units are extremelyrarely known. In these polyarylenes, it has been sought to introducesubstituents freely into the central arylene of the terarylene unit andmodify the terarylene in various ways.

For example, Japanese Patent Unexamined Publication (Laid-open) No.9-309945 discloses polyphenylene copolymers. According to this patentpublication, polyphenylene copolymers are synthesized using varioustypes of monoarylenes as recurring units.

Now, an object of the present invention is to provide polyarylenescontaining a terarylene as the recurring unit.

In a first aspect of the present invention, there are providedpolyarylenes comprising a recurring unit represented by formula (I) or(II) below:

(wherein:

Ar¹ and Ar² which may be the same or different, each representsindependently an arylene having 4 to 18 carbon atoms, which may besubstituted and may contain 1 to 5 nitrogen atoms;

R¹ and R², which may be the same or different, each representsindependently a C₁-C₂₀ hydrocarbon group which may optionally besubstituted, a C₁-C₂₀ alkoxy group which may optionally be substituted,a C₆-C₂₀ aryloxy group which may optionally be substituted, an aminegroup, hydroxy group or a group shown by formula: —Si(R³)(R⁴)(R⁵)(wherein R³, R⁴ and R⁵, which may be the same or different, eachrepresents independently a C₁-C₂₀ alkyl group, a C₆-C₂₀ arylalkyl group,a C₁-C₂₀ alkoxy group or a C₆-C₂₀ arylalkyloxy group)

provided that, in the recurring unit of formula (I), R¹ and R² may formtogether a C₄-C₂₀ saturated or unsaturated ring which may be intervenedby an oxygen atom and may be substituted;

A¹ and A², which may be the same or different, each represents hydrogenatom; a C₁-C₂₀ hydrocarbon group which may optionally be substituted; aC₁-C₂₀ alkoxy group which may optionally be substituted; a C₆-C₂₀aryloxy group which may optionally be substituted; a C₆-C₂₀ alkylaryloxygroup which may optionally be substituted; a C₁-C₂₀ alkoxycarbonyl groupwhich may optionally be substituted; a C₆-C₂₀ aryloxycarbonyl groupwhich may optionally be substituted; cyano group (—CN); carbamoyl group(—C(═O)NH₂); a haloformyl group (—C(═O)—X, wherein X is a halogen atom);or formyl group (—C(═O)—H); and,

n is an integer of 2 or more).

In the present invention, preferably, A¹ and A², which may be the sameor different, each represents independently a phenylene group which mayoptionally be substituted.

Also, the recurring unit is preferably a recurring unit shown by formula(I) described above, wherein R¹ and R² may form together a C₄-C₂₀saturated or unsaturated ring which may be intervened by an oxygen atomand may optionally be substituted.

Furthermore, the C₁-C₂₀ hydrocarbon group is preferably a linear orbranched C₁-C₂₀ alkyl group, a linear or branched C₂-C₂₀ alkenyl group,a linear or branched C₂-C₂₀ alkynyl group, a linear or branched C₃-C₂₀allyl group, a linear or branched C₄-C₂₀ alkadienyl group, a linear orbranched C₄-C₂₀ polyenyl group, a C₆-C₁₈ aryl group, a C₆-C₂₀ alkylarylgroup, a C₆-C₂₀ arylalkyl group, a C₄-C₂₀ cycloalkyl group, or a C₄-C₂₀cycloalkenyl group.

In a further aspect of the invention, there is provided a polyarylenecomprising a recurring unit represented by the formula (I) below:

(wherein:

Ar¹ and Ar², which may be the same or different, each representsindependently a paraarylene having 4 to 18 carbon atoms, which may besubstituted and may contain 1 to 5 nitrogen atoms;

R¹ and R², which may be the same or different, each representsindependently a C₁-C₂₀ hydrocarbon group which may be substituted, aC₁-C₂₀ alkoxy group which may be substituted, a C₆-C₂₀ aryloxy groupwhich may be substituted, an amine group, hydroxy group or a group shownby formula: —Si(R³)(R⁴)(R⁵) (wherein R³, R⁴ and R⁵, which may be thesame or different, each represents independently a C₁-C₂₀ alkyl group, aC₆-C₂₀ arylalkyl group, a C₁-C₂₀ alkoxy group or a C₆-C₂₀ arylalkyloxygroup);

provided that, in the recurring unit of formula (I), R¹ and R² may formtogether a C₄-C₂₀ saturated or unsaturated ring which may be intervenedby an oxygen atom and may be substituted;

A¹ and A², which may be the same or different, each representsindependently hydrogen atom; a C₁-C₂₀ hydrocarbon group which may besubstituted; a C₁-C₂₀ alkoxy group which may be substituted; a C₆-C₂₀aryloxy group which may be substituted; a C₆-C₂₀ alkylaryloxy groupwhich may be substituted; an alkoxycarbonyl group which may besubstituted; a C₆-C₂₀ aryloxycarbonyl group which may be substituted;cyano group (—CN); carbamoyl group (—C(═O)NH₂); a haloformyl group(—C(═O)—X, wherein X is a halogen atom); or formyl group (—C(═O)—H);and,

n is an integer of 2 or more).

In the present invention, preferably, A¹ and A², which may be the sameor different, each represents independently a paraphenylene group whichmay optionally be substituted.

Also, the recurring unit is preferably a recurring unit shown by formula(I) described above, wherein R¹ and R² form together a C₄-C₂₀ saturatedor unsaturated ring which may be intervened by an oxygen atom and may besubstituted.

Furthermore, the C₁-C₂₀ hydrocarbon group is preferably a linear orbranched C₁-C₂₀ alkyl group, a linear or branched C₂-C₂₀ alkenyl group,a linear or branched C₂-C₂₀ alkynyl group, a linear or branched C₃-C₂₀allyl group, a linear or branched C₄-C₂₀ alkadienyl group, a linear orbranched C₄-C₂₀ polyenyl group, a C₆-C₁₈ aryl group, a C₆-C₂₀ alkylarylgroup, a C₆-C₂₀ arylalkyl group, a C₄-C₂₀ cycloalkyl group, or a C₄-C₂₀cycloalkenyl group.

In a further aspect of the invention, there is provided a resincomposition comprising the polyarylene described above and a syntheticorganic polymer.

In a further aspect of the invention, there is provided a teraryl shownby formula (III) or (IV) below:

(wherein

Ar¹ and Ar², which may be the same or different, each representsindependently an arylene having 4 to 18 carbon atoms, which may besubstituted and may contain 1 to 5 nitrogen atoms;

R¹ and R², which may be the same or different, each representsindependently a C₁-C₂₀ hydrocarbon group which may optionally besubstituted, a C₁-C₂₀ alkoxy group which may optionally be substituted,a C₆-C₂₀ aryloxy group which may optionally be substituted, an aminegroup, hydroxy group or a group shown by formula: —Si(R³)(R⁴)(R⁵)(wherein R³, R⁴ and R⁵, which may be the same or different, eachrepresents independently a C₁-C₂₀ alkyl group, a C₆-C₂₀ arylalkyl group,a C₁-C₂₀ alkoxy group or a C₆-C₂₀ arylalkyloxy group)

provided that, in the recurring unit of formula (III), R¹ and R² mayform together a C₄-C₂₀ saturated or unsaturated ring which may beintervened by an oxygen atom and may optionally be substituted;

A¹ and A², which may be the same or different, each representsindependently hydrogen atom; a C₁-C₂₀ hydrocarbon group which mayoptionally be substituted; a C₁-C₂₀ alkoxy group which may optionally besubstituted; a C₆-C₂₀ aryloxy group which may optionally be substituted;a C₆-C₂₀ alkylaryloxy group which may optionally be substituted; aC₁-C₂₀ alkoxycarbonyl group which may optionally be substituted; aC₆-C₂₀ aryloxycarbonyl group which may optionally be substituted; cyanogroup (—CN); carbamoyl group (—C(═O)NH₂); a haloformyl group (—C(═O)—X,wherein X is a halogen atom); or formyl group (—C(═O)—H); and,

X¹ and X², which may be the same or different, each representsindependently a leaving group).

In a still further aspect of the present invention, there is provided aprocess for producing a polyarylene of formula (I) or (II) below:

(wherein:

Ar¹ and Ar², which may be the same or different, each representsindependently an arylene having 4 to 18 carbon atoms, which may besubstituted and may contain 1 to 5 nitrogen atoms;

R¹ and R², which may be the same or different, each representsindependently a C₁-C₂₀ hydrocarbon group which may optionally besubstituted, a C₁-C₂₀ alkoxy group which may optionally be substituted,a C₆-C₂₀ aryloxy group which may optionally be substituted, an aminegroup, hydroxy group or a group shown by formula: —Si(R³)(R⁴)(R⁵)(wherein R³, R⁴ and R⁵, which may be the same or different, eachrepresents independently a C₁-C₂₀ alkyl group, a C₆-C₂₀ arylalkyl group,a C₁-C₂₀ alkoxy group or a C₆-C₂₀ arylalkyloxy group);

provided that, in the recurring unit of formula (I), R¹ and R² may formtogether a C₄-C₂₀ saturated or unsaturated ring which may be intervenedby an oxygen atom and may be substituted;

A¹ and A², which may be the same or different, each representsindependently hydrogen atom; a C₁-C₂₀ hydrocarbon group which mayoptionally be substituted; a C₁-C₂₀ alkoxy group which may optionally besubstituted; a C₆-C₂₀ aryloxy group which may optionally be substituted;a C₆-C₂₀ alkylaryloxy group which may optionally be substituted; aC₁-C₂₀ alkoxycarbonyl group which may optionally be substituted; aC₆-C₂₀ aryloxycarbonyl group which may optionally be substituted; cyanogroup (—CN); carbamoyl group (—C(═O)NH₂); a haloformyl group (—C(═O)—X,wherein X is a halogen atom); or formyl group (—C(═O)—H); and,

n is an integer of 2 or more), which comprises polymerizing a terarylrepresented by formula (III) or (IV) below:

(wherein

Ar¹, Ar², R¹, R², A¹ and A² have the same significance as defined above;and,

X¹ and X², which may be the same or different, each representsindependently a leaving group).

In a further aspect of the present invention, there is provided aprocess for producing a teraryl, which comprises reacting ametallacyclopentadiene represented by formula (V) or (VI) below:

(wherein:

M is a metal from Groups III-V or the lanthanide series of the PeriodicTable;

L¹ and L², which may be the same or different, each representsindependently an anionic ligand, provided that L¹ and L² may becrosslinked;

Ar¹ and Ar², which may be the same or different, each representsindependently an arylene having 4 to 18 carbon atoms, which may besubstituted and may contain 1 to 5 nitrogen atoms;

R¹ and R², which may be the same or different, each representsindependently a C₁-C₂₀ hydrocarbon group which may optionally besubstituted, a C₁-C₂₀ alkoxy group which may optionally be substituted,a C₆-C₂₀ aryloxy group which may optionally be substituted, an aminegroup, hydroxy group or a group shown by formula: —Si(R³)(R⁴)(R⁵)(wherein R³, R⁴ and R⁵, which may be the same or different, eachrepresents a C₁-C₂₀ alkyl group, a C₆-C₂₀ arylalkyl group, a C₁-C₂₀alkoxy group or a C₆-C₂₀ arylalkyloxy group).

provided that, in the metallacyclopentadiene shown by formula (V), R¹and R² may form together a C₄-C₂₀ saturated or unsaturated ring whichmay be intervened by an oxygen atom and may optionally be substituted;and,

X¹ and X², which may be the same or different, each representsindependently a leaving group);

with an alkyne derivative represented by formula (VII) below:

A^(1a)—C≡C—A^(2a)  (VII)

 (wherein;

A^(1a) and A^(2a), which may be the same or different, each representsindependently hydrogen atom; a C₁-C₂₀ hydrocarbon group which mayoptionally be substituted; a C₁-C₂₀ alkoxy group which may optionally besubstituted; a C₆-C₂₀ aryloxy group which may optionally be substituted;a C₆-C₂₀ alkylaryloxy group which may optionally be substituted; aC₁-C₂₀ alkoxycarbonyl group which may optionally be substituted; aC₆-C₂₀ aryloxycarbonyl group which may optionally be substituted; aC₆-C₂₀ aryloxy group which may optionally be substituted; a C₆-C₂₀alkylaryloxy group which may optionally be substituted; or cyano group(—CN);

to produce a teraryl represented by formula (IIIa) or (IVa) below:

 (wherein each of Ar¹, Ar², R¹, R², A^(1a), A^(2a), X¹ and X² has thesame significance as defined above).

In the present invention, preferably, M is a metal from Group IV or thelanthanide series of the Periodic Table; the anionic ligand isnon-localized cyclic η⁵-coordination type ligand, a C₁-C₂₀ alkoxy group,a C₆-C₂₀ aryloxy group or a dialkylamide group.

The non-localized cyclic η⁵-coordination type ligand described above ispreferably a cyclopentadienyl, indenyl, fluorenyl or azulenyl group,which may be substituted.

Furthermore, the reaction preferably proceeds in the presence of acompound containing a metal from Groups IX-XV of the Periodic Table.

In a still further aspect of the invention, there is provided a processfor producing a polyarylene, which comprises reacting ametallacyclopentadiene represented by formula (V) or (VI) below:

(wherein:

Ar¹ and Ar², which may be the same or different, each representsindependently an arylene having 4 to 18 carbon atoms, which may besubstituted and may contain 1 to 5 nitrogen atoms;

R¹ and R², which may be the same or different, each representsindependently a C₁-C₂₀ hydrocarbon group which may be substituted, aC₁-C₂₀ alkoxy group which may be substituted, a C₆-C₂₀ aryloxy groupwhich may be substituted, an amine group, hydroxy group or a group shownby formula: —Si(R³)(R⁴)(R⁵) (wherein R³, R⁴ and R⁵, which may be thesame or different, each represents independently a C₁-C₂₀ alkyl group, aC₆-C₂₀ arylalkyl group, a C₁-C₂₀ alkoxy group or a C₆-C₂₀ arylalkyloxygroup);

provided that, in the metallacyclopentadiene shown by formula (V), R¹and R² may form together a C₄-C₂₀ saturated or unsaturated ring whichmay be intervened by an oxygen atom and may be substituted;

M is a metal from Groups III-V or the lanthanide series of the PeriodicTable;

L¹ and L², which may be the same or different, each representsindependently an anionic ligand, provided that L¹ and L² may becrosslinked; and,

X¹ and X², which may be the same or different, each representsindependently a leaving group);

with an alkyne derivative represented by formula (VII) below:

A^(1a)—C≡C—A^(2a)  (VII)

 (wherein;

A^(1a) and A^(2a), which may be the same or different, each representsindependently hydrogen atom; a C₁-C₂₀ hydrocarbon group which may besubstituted; a C₁-C₂₀ alkoxy group which may be substituted; a C₆-C₂₀aryloxy group which may be substituted; C₆-C₂₀ alkylaryloxy group whichmay be substituted; C₁-C₂₀ alkoxycarbonyl group which may besubstituted; a C₆-C₂₀ aryloxycarbonyl group which may be substituted; orcyano group (—CN); to produce a teraryl represented by formula (IIIa) or(IVa) below:

 (wherein each of Ar¹, Ar², R¹, R², A^(1a), A^(2a), X¹ and X² has thesame significance as defined above); and polymerizing the resultingteraryl to produce the polyarylene represented by formula (Ia) or (IIa)below:

 (wherein each of Ar¹, Ar², R¹, R², A^(1a) and A^(2a) has the samesignificance as defined above; and n is an integer of 2 or more).

In the present invention, preferably, M is a metal from Group IV or thelanthanide series of the Periodic Table; the anionic ligand isnon-localized cyclic η⁵-coordination type ligand, a C₁-C₂₀ alkoxy group,a C₆-C₂₀ aryloxy group or a dialkylamide group.

The non-localized cyclic η⁵-coordination type ligand described above ispreferably a cyclopentadienyl, indenyl, fluorenyl or azulenyl group,which may be substituted.

Furthermore, the reaction preferably proceeds in the presence of acompound containing a metal from Groups IX-XV of the Periodic Table.

In a still further aspect of the present invention, here is provided ametallacyclopentadiene represented by formula (V) or (VI) below:

(wherein:

M is a metal from Groups III-V or the lanthanide series of the PeriodicTable;

L¹ and L², which may be the same or different, each representsindependently an anionic ligand, provided that L¹ and L² may becrosslinked;

Ar¹ and Ar², which may be the same or different, each representsindependently an arylene having 4 to 18 carbon atoms, which may besubstituted and may contain 1 to 5 nitrogen atoms;

R¹ and R², which may be the same or different, each representsindependently a C₁-C₂₀ hydrocarbon group which may optionally besubstituted, a C₁-C₂₀ alkoxy group which may optionally be substituted,a C₆-C₂₀ aryloxy group which may optionally be substituted, an aminegroup, hydroxy group or a group shown by formula: —Si(R³)(R⁴)(R⁵)(wherein R³, R⁴ and R⁵, which may be the same or different, eachrepresents independently a C₁-C₂₀ alkyl group, a C₆-C₂₀ arylalkyl group,a C₁-C₂₀ alkoxy group or a C₆-C₂₀ arylalkyloxy group);

provided that, in the metallacyclopentadiene shown by formula (V), R¹and R² may form together a C₄-C₂₀ saturated or unsaturated ring whichmay be intervened by an oxygen atom and may be substituted; and,

X¹ and X², which may be the same or different, each representsindependently a leaving group).

PREFERRED EMBODIMENTS OF THE INVENTION

In one aspect of the present invention, the polyarylenes represented byformula (I) or (II) described above are provided.

Ar¹ and Ar², which may be the same or different, each representsindependently an arylene having 4 to 18 carbon atoms, which may besubstituted and may contain 1 to 5 nitrogen atoms. Ar¹ and Ar² arepreferably 5- to 18-membered, more preferably, 6- to 14-membered. Wherethe arylene contains nitrogen atoms, the number of nitrogen atoms ispreferably 1 to 3, more preferably 1 or 2.

The arylene may be a carbon ring or may be a heterocyclic ringcontaining 1 to 5 nitrogen atoms. The arylene may be a monocyclic ringor a condensed ring. Examples of the arylene include phenylenes (1,3-and 1,4-phenylenes), 5-amino-1,3-phenylene, 4-benzoyl-1,3-phenylene,5-benzoyl-1,3-phenylene, 2-benzoyl-1,4-phenylene, 4,4′-biphenyldiyl,2-carboxy-methyl-1,4-phenylene, 4-carboxymethyl-1,3-phenylene,5-carboxymethyl-1,3-phenylene, 1,3-naphthalenediyl, 1,4-naphthalenediyl,5-phenoxy-1,3-phenylene, 2-phenyl-1,3-phenylene, 4-phenyl-1,3-phenylene,5-phenyl-1,3-phenylene, 2-phenyl-1,4-phenylene, 2,6-pyridinediyl,2,4-pyridinediyl, 3,5-pyridinediyl, 3,6-pyridinediyl, 5,8-quinolinediyl,2,4-toluenediyl, 2,5-xylenediyl and so on. As isomers of the arylenesother than those at the 1,3- and 1,4-positions, which are not describedabove, there are, e.g., 2,4-quinolinediyl, 2,5-quinolinediyl,2,6-quinolinediyl, and the like. Preferred examples of the arylenes arephenylene, naphthalenediyl and pyridinediyl, which may optionally besubstituted, and more preferably, phenylene and naphthalenediyl whichmay optionally be substituted.

Examples of substituents on the arylenes shown by Ar¹ and Ar² are aC₁-C₂₀ hydrocarbon group, a C₁-C₂₀ alkoxy group, a C₆-C₂₀ aryloxy group,an amine group, hydroxy group or a group shown by formula:—Si(R³)(R⁴)(R⁵) (wherein R³, R⁴ and R⁵, which may be the same ordifferent, each represents independently a C₁-C₂₀ alkyl group, a C₆-C₂₀arylalkyl group, a C₁-C₂₀ alkoxy group or a C₆-C₂₀ arylalkyloxy group)

The substituents on the arylenes are not limited to those given above,so long as they are substituents that can be introduced into thearylenes prior to or after the formation of a teraryl as the monomer,and unless they interfere with the reaction. Furthermore, by introducingan appropriate protecting group, various substituents can be introducedinto the arylenes by publicly known reactions for ordinary aromaticcompounds, for example, through nucleophilic substitution.

R¹ and R², which may be the same or different, each representsindependently a C₁-C₂₀ hydrocarbon group which may optionally besubstituted, a C₁-C₂₀ alkoxy group which may optionally be substituted,a C₆-C₂₀ aryloxy group which may optionally be substituted, an aminegroup, hydroxy group or a group shown by formula: —Si(R³)(R⁴)(R⁵(wherein R³, R⁴ and R⁵, which may be the same or different, eachrepresents independently a C₁-C₂₀ alkyl group, a C₆-C₂₀ arylalkyl group,a C₁-C₂₀ alkoxy group or a C₆-C₂₀ arylalkyloxy group)

In the specification, the C₁-C₂₀ hydrocarbon group may be a saturated orunsaturated acyclic hydrocarbon or a saturated or unsaturated cyclichydrocarbon. Where the C₁-C₂₀ hydrocarbon group is acyclic, the groupmay be linear or branched. Examples of the C₁-C₂₀ hydrocarbon groupinclude a C₁-C₂₀ alkyl group, a C₂-C₂₀ alkenyl group, a C₂-C₂₀ alkynylgroup, a C₃-C₂₀ allyl group, a C₄-C₂₀ alkadienyl group, a C₄-C₂₀polyenyl group, a C₆-C₁₈ aryl group, a C₆-C₂₀ alkylaryl group, a C₆-C₂₀arylalkyl group, a C₄-C₂₀ cycloalkyl group, and a C₄-C₂₀ cycloalkenylgroup.

Examples of the alkyl group which is useful to practice the inventioninclude, but are not limited to, methyl, ethyl, propyl, n-butyl,t-butyl, dodecanyl, trifluoromethyl, perfluoro-n-butyl,2,2,2-trifluoroethyl, benzyl, 2-phenoxyethyl, etc.

Examples of the aryl group which is useful to practice the inventioninclude, but are not limited to, phenyl, 2-tolyl, 3-tolyl, 4-tolyl,naphthyl, biphenyl, 4-phenoxyphenyl, 4-fluorophenyl,3-carbomethoxyphenyl, 4-carbomethoxyphenyl, etc.

Examples of the alkoxy group which is useful to practice the inventioninclude, but are not limited to, methoxy, ethoxy, 2-methoxyethoxy,t-butoxy, etc. Examples of the aryloxy group which is useful to practicethe invention include, but are not limited to, phenoxy, naphthoxy,phenylphenoxy, 4-methylphenoxy, etc.

Examples of the amine group which is useful to practice the inventioninclude, but are not limited to, amino, dimethylamino, methylamino,methylphenylamino, phenylamino, etc.

Examples of the group shown by formula: —Si(R³)(R⁴)(R⁵) include, but arenot limited to, trimethylsilyl, triethylsilyl, trimethoxysilyl,triethoxysilyl, diphenylmethylsilyl, triphenylsilyl, triphenoxysilyl,dimethylmethoxysilyl, dimethylphenoxysilyl, methylmethoxyphenyl, etc.

Substitutents may be introduced into the C₁-C₂₀ hydrocarbon group,C₁-C₂₀ alkoxy group, and C₆-C₂₀ aryloxy group. Examples of thesubstituents are a halogen atom, hydroxy group, amino group, etc.

In the recurring unit shown by formula (I), however, R¹ and R² may formtogether a C₄-C₂₀ saturated or unsaturated ring which may be intervenedby an oxygen atom and may be substituted. Preferably, The ring is a 4-to 16-membered ring, more preferably a 4- to 12-membered ring. The ringmay optionally be substituted with substituents such as a C₁-C₂₀hydrocarbon group, a C₁-C₂₀ alkoxy group, a C₆-C₂₀ aryloxy group, anamine group, hydroxy group or a group shown by formula: —Si(R³)(R⁴)(R⁵)(wherein R³, R⁴ and R⁵, which may be the same or different, eachrepresents independently a C₁-C₂₀ alkyl group, a C₆-C₂₀ arylalkyl group,a C₁-C₂₀ alkoxy group or a C₆-C₂₀ arylalkyloxy group), etc.

A¹ and A², which may be the same or different, each representsindependently hydrogen atom; a C₁-C₂₀ hydrocarbon group which mayoptionally be substituted; a C₁-C₂₀ alkoxy group which may optionally besubstituted; a C₆-C₂₀ aryloxy group which may optionally be substituted;a C₆-C₂₀ alkylaryloxy group which may optionally be substituted; aC₁-C₂₀ alkoxycarbonyl group which may optionally be substituted; aC₆-C₂₀ aryloxycarbonyl group which may optionally be substituted; cyanogroup (—CN); carbamoyl group (—C(═O)NH₂); a haloformyl group (—C(═O)—X,wherein X is a halogen atom); or formyl group (—C(═o)—H). The C₁-C₂₀hydrocarbon group, the C₁-C₂₀ alkoxy group which may optionally besubstituted, the C₆-C₂₀ aryloxy group which may optionally besubstituted and the amino group are the same as those given for R¹ andR².

Examples of the alkoxycarbonyl group which is useful to practice theinvention include, but are not limited to, methoxycarbonyl,ethoxycarbonyl, 2-methoxyethoxycarbonyl, t-butoxycarbonyl, etc.

Examples of the aryloxycarbonyl group which is useful to practice theinvention include, but are not limited to, phenoxycarbonyl,naphthoxycarbonyl, phenylphenoxycarbonyl, 4-methylphenoxycarbonyl, etc.

Carbamoyl group (—C(═O)NH₂), the haloformyl group (—C(═O)—X, wherein Xis a halogen atom), formyl group (—C(═O)—H) or the like can be mutuallyconverted into cyano group or an alkoxycarbonyl group.

The polyarylenes of the present invention may also be copolymers. Inaddition to the terarylene recurring units described above, thepolyarylenes may contain, e.g., one or more other recurring units. Theother recurring unit may be an arylene. Examples of the arylene includephenylenes (1,3- and 1,4-phenylenes), 5-amino-1,3-phenylene,4-benzoyl-1,3-phenylene, 5-benzoyl-1,3-phenylene,2-benzoyl-1,4-phenylene, 4,4′-biphenyldiyl,2-carboxy-methyl-1,4-phenylene, 4-carboxymethyl-1,3-phenylene,5-carboxymethyl-1,3-phenylene, 1,3-naphthalenediyl, 1,4-naphthalenediyl,5-phenoxy-1,3-phenylene, 2-phenyl-1,3-phenylene, 4-phenyl-1,3-phenylene,5-phenyl-1,3-phenylene, 2-phenyl-1,4-phenylene, 2,6-pyridinediyl,2,4-pyridinediyl, 3,5-pyridinediyl, 3,6-pyridinediyl, 5,8-quinolinediyl,2,4-toluenediyl, 2,5-xylenediyl and so on. As isomers of the arylenesother than those at the 1,3- and 1,4-positions, which are not describedabove, there are, e.g., 2,4-quinolinediyl, 2,5-quinolinediyl,2,6-quinolinediyl, and the like.

In other aspect of the present invention, there is provided a resincomposition, e.g., a blend, comprising the polyarylene and a syntheticorganic polymer. For example, there is provided a resin compositioncomprising 1 to 99 wt % of the polyarylene and 99 to 1 wt % of thesynthetic organic polymer. There is also provided 10 to 90 wt %of thepolyarylene and 90 to 10 wt % of the synthetic organic polymer.

The synthetic organic polymer includes a thermoplastic polymer, athermosetting polymer, engineering plastics, etc. The synthetic organicpolymer may also be a copolymer. Examples of the thermoplastic polymerare polyolefin such as polyethylene, polypropylene, polycycloolefin,ethylene-propylene copolymer, etc.; polyvinyl chloride, polyvinylidenechloride, polyvinyl acetate, polyacrylic acid, polymethacrylic acid,polystyrene, polyamide, polyester, polycarbonate, etc. Examples of thethermosetting polymer are phenol resin, urea resin, melamine resin,alkyd resin, unsaturated polyester resin, epoxy resin, silicone resinand polyurethane resin. Examples of the engineering plastics includepolyimide, polyphenylene oxide, polysulfone, etc. The synthetic organicpolymer may be synthetic rubber such as styrene-butadiene, etc., orfluorine resin such as polytetrafluoroethylene, etc.

The resin composition may also contain a variety of additives. Examplesof the additives are plasticizers, antistatic agents, coloring agents,etc. The resin composition may further contain reinforcing agents suchas glass fibers, carbon fibers, etc.

The polyarylene or resin composition in accordance with the presentinvention can be prepared into the shape of fibers, films or sheetsusing methods publicly known to one skilled in the art. Examples of suchmethods include, but are not limited to, melt spinning, spinning from asolution, dry jet wet spinning, extrusion, flow casting and molding. Thefibers, films or sheets are further processed by means of calendermolding, embossing, forming or other means publicly known to one skilledin the art.

In a still further aspect of the present invention, there is provided ateraryl represented by formula (III) or (IV). In formula (III) or (IV),Ar¹, Ar², R¹, R², A¹ and A² have the same significance as defined above.

X¹ and X², which may be the same or different, each representsindependently a leaving group. Examples of the leaving group are ahalogen atom such as F, Cl, Br or I, p-toluenesulfonyl group, etc., withparticular preference being Br.

In a still further aspect of the present invention, there is provided aprocess for producing the polyarylene represented by formula (I) or (II)described above. This reaction is shown by the following equation:

(wherein Ar¹, Ar², R¹, R², A¹, A², X¹ and X² have the same significanceas defined above);

(wherein Ar¹, Ar², R¹, R², A¹, A², X¹ and X² have the same significanceas defined above).

Polymerization is carried out by coupling monomers through removal ofthe leaving groups X¹ and X² with a reducing agent. As the reducingagent, e.g., metals from Groups I-XIV of the Periodic Table can bewidely employed. Examples of the reducing agent include metals fromGroup I of the Periodic Table such as lithium or sodium; metals fromGroup II such as magnesium; metals from Group XI such as copper; andmetals from Group XII such as zinc.

The polymers of the present invention can be formed by polymerization ofmonomers described above through reductive coupling using a nickel (0)compound described in T. Kanbara, T. Kushida, N. Saito, I. Kuwajima, K.Kubota and T. Yamamoto, Chemistry Letters, 1992, 583-586, or throughnickel catalyst-reductive coupling described in U.S. Pat. Nos. 5,227,457or 5,241,044.

That is, where a mild reducing agent such as magnesium or zinc is used,an organic metal complex catalyst such asbis(triphenylphosphine)dichloronickel ordichloro(2,2′-bipyridine)nickel, PdCl₂(2,2′-bipyridine) may be employed,since polymerization proceeds under relatively mild conditions.Nitrogen-containing compounds such as bipyridine, orphosphorus-containing organic compounds such as phosphine may also beco-present as a co-catalyst.

As examples of the organic metal complex, those consisting of thecentral metal from Groups III-XI, preferably from Groups VI-XI of thePeriodic Table, with ligands such as a phosphine; an aromatic amine suchas pyridine or bipyridine, a halogen atom, etc. are preferably employed.Preferably, the central metal takes so-called tetra- to hexa-valentcoordination and more preferably, is a metal from Group X of thePeriodic Table. Examples of the phosphine include, but are not limitedto, triphenylphosphine and methyldiphenylphosphine.

Polymerization using magnesium as a reducing agent is described in T.Yamamoto et al., Bull. Chem. Soc. Jpn., 1978, 51, 2091, T. Yamamoto,Prog. Polym. Sci., 1992, 17, 1155, and M. Rehahan et al., Polymer, 1989,30, 1054.

Polymerization using zinc as a reducing agent is described in, e.g., T.Yamamoto et al., Makromol. Chem., 1989, 190, 1649, M. Ueda et al.,Macromolecules, 1990, 23, 926, I. Colon et al., J. Polym. Sci., Polym.Chem. Ed., 1990, 28, 367, M. Ueda et al., J. Polym. Sci., Chem. Ed.,1992, 30, 1567, V. Chaturvede et al., and J. Chem. Soc., Chem. Commun.,1992, 1658.

The polymerization is carried out preferably at temperatures from −80°C. to 300° C., more preferably at 0° C. to 150° C. Pressure is appliedin the range of 0.1 bar to 2500 bars, preferably 0.5 bar to 10 bars. Thepolymerization can be carried out continuously or batch-wise, in onestep or in a multi-step, in a solution or a suspension, in a gaseousphase or in a supercritical medium.

As a solvent, an aliphatic or aromatic solvent can be used; preferably,a polar solvent is employed. Examples of the solvent are an etherealsolvent such as tetrahydrofuran or diethyl ether, a halogenatedhydrocarbon such as methylene chloride, a halogenated aromatichydrocarbon such as o-dichlorobenzene, an amide such asN,N-dimethylformamide, and a sulfoxide such as dimethylsulfoxide.

In a still further aspect of the present invention, there is provided aprocess for producing a teraryl represented by formula (IIIa) or (IVa)described above. This reaction is shown by the following equation:

(wherein Ar¹, Ar², R¹, R², A¹², A²², X¹ and X² have the samesignificance as defined above);

(wherein Ar¹, Ar², R¹, R², A^(1a), A^(2a), X¹ and X² have the samesignificance as defined above);

The reaction is carried out preferably in the presence of a catalyst. Asthe catalyst there can be used metal compounds from Groups IV-XV of thePeriodic Table, particularly metal compounds from Groups VIII-XV of thePeriodic Table. For example, metal salts such as CuX, NiX₂ or BiX₃(wherein X is a halogen atom such as chlorine or bromine atom) areemployed. Alternatively, the organometallic complexes, especially anickel complex, which are herein exemplified in the description on thepolymerization may be employed.

The formation of a benzene ring by reacting a metallacyclopentadienesuch as zirconacyclopentadiene with an acetylene derivative in thepresence of CuCl is described in T. Takahashi et al., J. Am. Chem. Soc.,1998, 120, 1672-1680.

Where at least one of A^(1a) and A^(2a) is an electron-donating groupsuch as an alkyloxycarbonyl group, an aryloxycarbonyl group, nitrilegroup, etc., a copper salt such as copper chloride is preferably used.On the other hand, where A^(1a) and A^(2a) are an alkyl group, an arylgroup, an alkoxy group, an aryloxy group, etc., a nickel complex ispreferably used.

When of A^(1a) and A^(2a) is cyano group or an alkoxycarbonyl group,this substituent can be converted into carbamoyl group (—C(═O)NH₂), ahaloformyl group (—C(═O)—X, wherein X is a halogen atom) or formyl group(—C(═O)—H).

The reaction is carried out preferably at temperatures from −80° C. to300° C., more preferably at −20° C. to 50° C. Pressure is applied in therange of 0.1 bar to 2500 bars, preferably 0.5 bar to 10 bars. Thereaction is preferably carried out in situ without separating themetallacyclopentadiene shown by formula (V) or (VI) described above.

In a still further aspect of the present invention, themetallacyclopentadiene shown by formula (V) or (VI) described above isprovided. The metallacyclopentadiene can be synthesized from ametallocene according to the following equation:

(wherein Ar¹, R¹, A¹, X¹, L¹ and L²have the same significance as definedabove; B is a crosslinking group; and Z¹ and Z², which may be the sameor different, each represents independently a ligand that can be splitoff);

 X¹—Ar¹—C≡C—B—C≡C—Ar²—X²  (VIIIb)

(wherein Ar¹, Ar², X¹, X², L¹ and L² have the same significance asdefined above; B is a crosslinking group; and Z¹ and Z², which may bethe same or different, each represents independently a ligand that canbe split off);

(wherein Ar¹, Ar², R¹, R², X¹, X², L¹ and L² have the same significanceas defined above; and Z¹ and Z², which may be the same or different,each represents a ligand that can be split off).

B is a crosslinking group and hydrocarbon group, which may be intervenedby, e.g., an oxygen atom, especially an alkylene group which may beintervened by an oxygen atom.

There is no restriction on Z¹ and Z², so long as they can be coordinatedwith M. Examples of Z¹ and Z² include a halogen atom, an olefin such asethylene, an alkyl group, and the like.

The reaction described above is carried out preferably at −120° C. to50° C., more preferably at −120° C. to 0° C., in the presence of astrong base such as an alkyl lithium. The formation ofmetallacyclopentadienes is described in, e.g., J. Am. Chem. Soc., 1994,116, 1880-1889.

As M, metal complexes containing metals from Group IV or the lanthanidemetal series of the Periodic Table are preferably employed. Metalcomplexes containing a non-localized cyclic η⁵-coordination type ligandare also preferred.

L¹ and L² are preferably a non-localized cyclic η⁵-coordination typeligand. Examples of the non-localized cyclic η⁵-coordination type ligandare unsubstituted cyclopentadienyl group and a substitutedcyclopentadienyl group. Examples of the substituted cyclopentadienylgroup include methylcyclopentadienyl, ethylcyclopentadienyl,isopropylcyclopentadienyl, t-butylcyclopentadienyl,dimethylcyclopentadienyl, diethylcyclopentadienyl,diisopropylcyclopentadienyl, di-t-butylcyclopentadienyl,tetramethylcyclopentadienyl, indenyl, 2-methylindenyl,2-methyl-4-phenylindenyl, tetrahydroindenyl, benzindenyl, fluorenyl,benzofluorenyl, tetrahydrofluorenyl and octahydrofluorenyl groups.

In the non-localized cyclic η⁵-coordination type ligand, one or moreatoms of the non-localized cyclic η⁵-coordination type may besubstituted for the hetero atom. The ligand may contain, in addition tohydrogen, one or more hetero atoms such as the elements from Group XIVand/or Groups XV, XVI and XVII, of the Periodic Table.

The non-localized cyclic η⁵-coordination type ligand, e.g., thecyclopentadienyl group may be crosslinked with the central metal by oneor more crosslinking ligands that may be cyclic. Examples of thecrosslinking ligands are CH₂, CH₂CH₂, CH(CH₃)CH₂, CH(C₄H₉)C(CH₃)₂,C(CH₃)₂, (CH₃)₂Si, (CH₃)₂Ge, (CH₃)₂Sn, (C₆H₅)₂Si, (C₆H₅)(CH₃)Si,(C₆H₅)₂Ge, (C₆H₅)₂Sn, (CH₂)₄Si, CH₂Si(CH₃)₂, o-C₆H₄ or 2,2′-(C₆H₄))₂.

Two or more non-localized cyclic η⁵-coordination type ligands, e.g., thecyclopentadienyl groups may be crosslinked with each other by one ormore crosslinking ligands that may be cyclic. Examples of thecrosslinking ligands are CH₂, CH₂CH₂, CH(CH₃)CH₂, CH(C₄H₉)C(CH₃)₂,C(CH₃)₂, (CH₃)₂Si, (CH₃)₂Ge, (CH₃)₂Sn, (C₆H₅)₂Si, (C₆H₅)(CH₃)Si,(C₆H₅)₂Ge, (C₆H₅)₂Sn, (CH₂)₄Si, CH₂Si(CH₃)₂, o-C₆H₄ or 2,2′-(C₆H₄)₂.

The metallacyclopentadienes of the present invention also embracecompounds containing two or more metallacyclopentadiene moieties. Suchcompounds are known as multinuclear metallocenes. The multinuclearmetallocenes described above may have any substitution mode or anycrosslinking mode. The independent metallocene moieties in themultinuclear metallocene may be the same or different. Examples of themultinuclear metallocenes are described in, e.g., EP-A-632063, JapanesePatent Unexamined Publication (Laid-open) Nos. 4-80214 and 4-85310 andEP-A-654476.

The metallacyclopentadienes of the present invention can be synthesizedusing, e.g., the metallocenes below.

In the case of dichloro-compounds such as

bis(indenyl)dichlorozirconium;

bis(fluorenyl)dichorozirconium;

(indenyl)(fluorenyl)dichlorozirconium;

bis(cyclopentadienyl)dichlorotitanium;

(dimethylsilanediyl)bis(indenyl)dichlorozirconium;

(dimethylsilanediyl)bis(tetrahydroindenyl)dichlorozirconium;(dimethylsilanediyl)(indenyl)dichlorozirconium;

(dimethylsilanediyl)bis(2-methylindenyl)dichlorozirconium;

(dimethylsilanediyl)bis(2-ethylindenyl)dichlorozirconium;

(dimethylsilanediyl)bis(2-methyl-4,5-benzindenyl)dichlorozirconium;

(dimethylsilanediyl)bis(2-ethyl-4,5-benzindenyl)dichlorozirconium;

(dimethylsilanediyl)bis(2-methyl-4-phenylindenyl)dichlorozirconium;

(dimethylsilanediyl)bis(2-ethyl-4-phenylindenyl)dichlorozirconium;

(dimethylsilanediyl)bis(2-methyl-4,6-diisopropylindenyl)dichlorozirconium;etc., the metallacyclopentadienes are formed either after reduction ofthese compounds with a strong base, e.g.,an alkali metal such as sodium,an alkaline earth metal such as magnesium, or after their conversioninto the corresponding dialkyl compounds. Examples of the metallocensare:

bis(cyclopentadienyl)dibutylzirconium;

bis(indenyl)dibutylzirconium;

bis(fluorenyl)dibutylzirconium;

(indenyl)(fluorenyl)dibutylzirconium;

(3-methyl-5-naphthylindenyl)(2,7-di-tert-butylfluorenyl)dibutylzirconium;

(3-methyl-5-naphthylindenyl)(3,4,7-trimethoxyfluorenyl)dibutylzirconium;

(pentamethylcyclopentadienyl)(tetrahydroindenyl)dibutylzirconium;

(cyclopentadienyl)(1-octene-8-ylcyclopentadienyl)dibutyzirconium;

(indenyl)(1-butene-4-ylcyclopentadienyl)dibutylzirconium;

[1,3-bis(trimethylsilyl)cyclopentadienyl](3,4-benzofluorenyl)dibutylzirconium;

bis(cyclopentadienyl)dibutyltitanium;

dimethylsilanediylbis(indenyl)dibutylzirconium;

dimethylsilanediylbis(tetrahydroindenyl)dibutylzirconium;

dimethylsilanediyl(cyclopentadienyl)(indenyl)dibutylzirconium;

dimethylsilanediylbis(2-methylindenyl)dibutylzirconium;

dimethylsilanediylbis(2-ethylindenyl)dibutylzirconium;

dimethylsilanediylbis(2-methyl-4,5-benzindenyl)dibutylzirconium;

dimethylsilanediylbis(2-ethyl-4,5-benzindenyl)dibutylzirconium;

dimethylsilanediylbis(4,5-dihydro-8-methyl-7H-cyclopent[e]acenaphthylene-7-ylidene)dibutylzirconium;

dimethylsilanediyl(2-methyl-4,5-benzindenyl)(2-methyl-4-phenylindenyl)dibutylzirconium;

dimethylsilanediyl(2-ethyl-4,5-benzindenyl)(2-methyl-4-phenylindenyl)dibutylzirconium;

dimethylsilanediyl(2-methyl-4,5-benzindenyl)(2-ethyl-4-phenylindenyl)dibutylzirconium;

dimethylsilanediyl(2-ethylindenyl)(2-ethyl-4-phenylnaphthyl)dibutylzirconium;

dimethylsilanediyl(2-methylindenyl)(4-phenylindenyl)dibutylzirconium;

dimethylsilanediylbis(2-methyl-4-phenylindenyl)dibutylzirconium;

dimethylsilanediylbis(2-ethyl-4-phenylindenyl)dibutylzirconium;

dimethylsilanediylbis(2-methyl-4,6-diisopropylindenyl)dibutylzirconium;

dimethylsilanediylbis(2-ethyl-4,6-diisopropylindenyl)dibutylzirconium;

dimethylsilanediylbis(2-methyl-4-naphthylindenyl)dibutyzirconium;

dimethylsilanediylbis(2-ethyl-4-naphthylindenyl)dibutylzirconium;

methylphenylsilanediylbis(indenyl)dibutylzirconium;

methylphenylsilanediyl(cyclopentadienyl)(indenyl)dibutylzirconium;

methylphenylsilanediylbis(tetrahydroindenyl)dibutylzirconium;

methylphenylsilanediylbis(2-methylindenyl)dibutylzirconium;

methylphenylsilanediylbis(2-ethylindenyl)dibutylzirconium;

methylphenylsilanediylbis(2-methyl-4,5-benzindenyl)dibutylzirconium;

methylphenylsilanediylbis(2-ethyl-4,5-benzindenyl)dibutylzirconium;

methylphenylsilanediylbis(4,5-dihydro-8-methyl-7H-cyclopent[e]acenaphthylene-7-ylidene)dibutylzirconium;

methylphenylsilanediyl(2-methyl-4,5-benzindenyl)(2-methyl-4-phenylindenyl)dibutylzirconium;

methylphenylsilanediyl(2-ethylindenyl)(2-methyl-4-phenylindenyl)dibutylzirconium;

methylphenylsilanediyl(2-methyl-4,5-benzindenyl)(2-ethyl1-4-phenylindenyl)dibutylzirconium;

methylphenylsilanediyl(2-ethyl-4,5-benzindenyl)(2-ethyl-indenyl)dibutylzirconium;

methylphenylsilanediyl(2-methylindenyl)(4-phenylindenyl)dibutylzirconium;

methylphenylsilanediylbis(2-methyl-4-phenylindenyl)dibutylzirconium;

methylphenylsilanediylbisdibutylzirconium;

methylphenylsilanediylbis(2-methyl-4,6-diisopropylindenyl)dibutylzirconium;

methylphenylsilanediylbis(2-ethyl-4,6-diisopropylindenyl)dibutylzirconium;

methylphenylsilanediylbis(4-naphthylindenyl)dibutylzirconium;

methylphenylsilanediylbis(2-ethyl-4-naphthylindenyl)dibutylzirconium;

diphenylsilanediylbis(indenyl)dibutylzirconium;

diphenylsilanediylbis(2-methylindenyl)dibutylzirconium;

diphenylsilanediylbis(2-ethylindenyl)dibutylzirconium;

diphenylsilanediyl(cyclopentadienyl)(indenyl)dibutylzirconium;

diphenylsilanediylbis(2-methyl-4,5-benzindenyl)dibutylzirconium;

diphenylsilanediylbis(2-ethyl-4,5-benzindenyl)dibutylzirconium;

diphenylsilanediyl(2-methyl-4,5-benzindenyl)(2-methyl-4-phenylindenyl)dibutylzirconium;

diphenylsilanediyl(2-ethyl-4,5-benzindenyl)(2-methyl-4-phenylindenyl)dibutylzirconium;

diphenylsilanediyl(2-methyl-4,5-benzindenyl)(2-ethyl-4-phenylindenyl)dibutylzirconium;

diphenylsilanediyl(2-ethyl-4,5-benzindenyl)(2-ethyl-4-naphthylindenyl)dibutylzirconium;

diphenylsilanediyl(2-methylindenyl)(4-phenylindenyl)dibutylzirconium;

diphenylsilanediylbis(2-methyl-4-phenylindenyl)dibutylzirconium;

diphenylsilanediylbis(2-ethyl-4-phenylindenyl)dibutylzirconium;

diphenylsilanediylbis(2-methyl-4,6-diisopropylindenyl)dibutylzirconium;

diphenylsilanediylbis(2-ethyl-4,6-diisopropylindenyl)dibutylzirconium;

diphenylsilanediylbis(2-methyl-4-naphthylindenyl)dibutyzirconium;

diphenylsilanediylbis(2-ethyl-4-naphthylindenyl)dibutylzirconium;

1-silacyclopentane-1,1-bis(indenyl)dibutylzirconium;

1-silacyclopentane-1,1-bis(2-methylindenyl)dibutylzirconium;

1-silacyclopentane-1,1-bis(2-ethylindenyl)dibutylzirconium;

1-silacyclopentane-1,1-bis(2-methyl-4,5-benzindenyl)dibutylzirconium;

1-silacyclopentane-1,1-bis(2-ethyl-4,5-benzindenyl)dibutylzirconium;

1-silacyclopentane-1-(2-methyl-4,5-benzindenyl)-1-(2-methyl-4-phenylindenyl)dibutylzirconium;

1-silacyclopentane-1-(2-ethyl-4,5-benzindenyl)-1-(2-methyl-4-phenylindenyl)dibutylzirconium;

1-silacyclopentane-1-(2-methyl-4,5-benzindenyl)-1-(2-ethyl-4-phenylindenyl)dibutylzirconium;

1-silacyclopentane-1-(2-ethyl-4,5-benzindenyl)-1-(2-ethyl-4-naphthylindenyl)dibutylzirconium;

1-silacyclopentane-1-(2-methylindenyl)-1-(4-phenylindenyl)dibutylzirconium;

1-silacyclopentane-1,1-bis(2-methyl-4-phenylindenyl)dibutylzirconium;

1-silacyclopentane-1,1-bis(2-ethyl-4-phenylindenyl)dibutylzirconium;

1-silacyclopentane-1,1-bis(2-methyl-4,6-diisopropylindenyl)dibutylzirconium;

1-silacyclopentane-1,1-bis(2-ethyl-4,6-diisopropylindenyl)dibutylzirconium;

1-silacyclopentane-1,1-bis(2-methyl-4-naphthylindenyl)dibutylzirconium;

1-silacyclopentane-1,1-bis(2-ethyl-4-naphthylindenyl)dibutylzirconium;

bis(cyclopentadienyl)dibutyltitanium;

ethylene-1,2-bis(indenyl)dibutylzirconium;

ethylene-1,2-bis(tetrahydroindenyl)dibutylzirconium;

ethylene-1-(cyclopentadienyl)-2-(1-indenyl)dibutylzirconium;

ethylene-1-(cyclopentadienyl)-2-(2-indenyl)dibutylzirconium;

ethylene-1-(cyclopentadienyl)-2-(2-methyl-1-indenyl)dibutylzirconium;

ethylene-1,2-bis(2-methylindenyl)dibutylzirconium;

ethylene-1,2-bis(2-ethylindenyl)dibutylzirconium;

ethylene-1,2-bis(2-methyl-4,5-benzindenyl)dibutylzirconium;

ethylene-1,2-bis(2-ethyl-4,5-benzindenyl)dibutylzirconium;

ethylene-1,2-bis(4,5-dihydro-8-methyl-7H-cyclopent[e]acenaphthylene-7-ylidene)dibutylzirconium;

ethylene-1-(2-methyl-4,5-benzindenyl)-2-(2-methyl-4-phenylindenyl)dibutylzirconium;

ethylene-1-(2-ethyl-4,5-benzindenyl)-2-(2-methyl-4-phenylindenyl)dibutylzirconium;

ethylene-1-(2-methyl-4,5-benzindenyl)-2-(2-ethyl-4-phenylindenyl)dibutylzirconium;

ethylene-1-(2-ethyl-4,5-benzindenyl)-2-(2-ethyl-4-naphthylindenyl)dibutylzirconium;

ethylene-1-(2-methylindenyl)-2-(4-phenylindenyl)dibutylzirconium;

ethylene-1,2-bis(2-methyl-4-phenylindenyl)dibutylzirconium;

ethylene-1,2-bis(2-ethyl-4-phenylindenyl)dibutylzirconium;

ethylene-1,2-bis(2-methyl-4,6-diisopropylindenyl)dibutylzirconium;

ethylene-1,2-bis(2-ethyl-4,6-diisopropylindenyl)dibutylzirconium;

ethylene-1,2-bis(2-methyl-4-naphthylindenyl)dibutylzirconium;

ethylene-1,2-bis(2-ethyl-4-naphthylindenyl)dibutylzirconium;

propylene-2,2-bis(indenyl)dibutylzirconium;

propylene-2-cyclopentadienyl-2-(1-indenyl)dibutylzirconium;

propylene-2-cyclopentadienyl-2-(4-phenyl-1-indenyl)dibutylzirconium;

propylene-2-cyclopentadienyl-2-(9-fluorenyl)dibutylzirconium;

propylene-2-cyclopentadienyl-2-(2,7-dimethoxy-9-fluorenyl)dibutylzirconium;

propylene-2-cyclopentadienyl-2-(2,7-di-tert-butyl-9-fluorenyl)dibutylzirconium;

propylene-2-cyclopentadienyl-2-(2,7-dibromo-9-fluorenyl)dibutylzirconium;

propylene-2-cyclopentadienyl-2-(2,7-diphenyl-9-fluoreny]dibutylzirconium;

propylene-2-cyclopentadienyl-2-(2,7-dimethyl-9-fluorenyl)dibutylzirconium;

propylene-2-(3-methylcyclopentadienyl)-2-(2,7-dibutyl-9-fluorenyl)dibutylzirconium;

propylene-2-(3-tert-butylcyclopentadienyl)-2-(2,7-dibutyl-9-fluorenyl)dibutylzirconium;

propylene-2-(3-trimethylsilylcyclopentadienyl)-2-(3,6-di-tert-butyl-9-fluorenyl)dibutylzirconium;

propylene-2-cyclopentadienyl-2-[2,7-bis(3-butene-1-yl)-9-fluorenyl]dibutylzirconium;

propylene-2-cyclopentadienyl-2-(3-tert-butyl-9-fluorenyl)dibutylzirconium;

propylene-2,2-bis(tetrahydroindenyl)dibutylzirconium;

propylene-2,2-bis(2-methylindenyl)dibutylzirconium;

propylene-2,2-bis(2-ethylindenyl)dibutylzirconium;

propylene-2,2-bis(2-methyl-4,5-benzindenyl)dibutylzirconium;

propylene-2,2-bis(2-ethyl-4,5-benzindenyl)dibutylzirconium;

propylene-2,2-bis(4,5-dihydro-8-methyl-7H-cyclopent[e]acenaphthylene-7-ylidene)dibutylzirconium;

propylene-2-(2-methyl-4,5-benzindenyl)-2-(2-methyl-4-phenylindenyl)dibutylzirconium;

propylene-2-(2-ethyl-4,5-benzindenyl)-2-(2-methyl-4-phenylindenyl)dibutylzirconium;

propylene-2-(2-methyl-4,5-benzindenyl)-2-(2-ethyl-4-phenylindenyl)dibutylzirconium;

propylene-2-(2-ethyl-4,5-benzindenyl)-2-(2-ethyl-4-naphthylindenyl)dibutylzirconium;

propylene-2-(2-methylindenyl)-2-(4-phenylindenyl)dibutyzirconium;

propylene-2,2-bis(2-methyl-4-phenylindenyl)dibutylzirconium;

propylene-2,2-bis(2-ethyl-4-phenylindenyl)dibutylzirconpropylene-2,2-bis(2-methyl-4,6-diisopropylindenyl)dibutylzirconium;

propylene-2,2-bis(2-ethyl-4,6-diisopropylindenyl)dibutylzirconium;

propylene-2,2-bis(2-methyl-4-naphthylindenyl)dibutylzirconium;

propylene-2,2-bis(2-ethyl-4-naphthylindenyl)dibutylzirconium;

1,6-bis[methylsilylbis(2-methyl-4-phenylindenyl)dibutylzirconium]hexane;

1,6-bis[methylsilylbis(2-methyl-4,5-benzindenyl)dibutylzirconium]hexane;

1,6-bis[methylsilylbis(2-ethyl-4-phenylindenyl)dibutylzirconium]hexane;

1,6-bis[methylsilylbis(2-methyl-4-naphthylindenyl)dibutylzirconium]hexane;

1,6-bis[methylsilylbis(2-methyl-4,6-diisopropylindenyl)dibutylzirconium]hexane;

1,6-bis[methylsilyl(2-methyl-4-phenylindenyl)(4,5-benzindenyl)dibutylzirconium]hexane;

1-[methylsilylbis(tetrahydroindenyl)dibutylzirconium]-6-[ethylstannyl(cyclopentadienyl)(fluorenyl)dibutylzirconium]hexane;

1,6-disila-1,1,6,6-tetramethyl-1,6-bis[methylsilylbis(2-methyl-4-phenylindenyl)dibutylzirconium]hexane;

1,4-disila-1,4-bis[methylsilylbis(2-methyl-4-phenylindenyl)dibutylzirconium]cyclohexane;

[1,4-bis(1-indenyl)-1,1,4,4-tetramethyl-1,4-disilabutane]bis(pentamethylcyclopentadienyldibutylzirconium);

[1,4-bis(9-fluorenyl)-1,1,4,4-tetramethyl-1,4-disilabutane]bis(cyclopentadienyldibutylzirconium);

[1,4-bis(1-indenyl)-1,1,4,4-tetramethyl-1,4-disilabutane]bis(cyclopentadienyldibutylzirconium);

[1-(1-indenyl)-6-(2-phenyl-1-indenyl)-1,1,6,6-tetraethyl-1,6-disila-4-oxahexane]bis(tert-butylcyclopentadienyldibutylzirconium);

[1,10-bis(2,3-dimethyl-1-indenyl)-1,1,10,10-tetramethyl-1,10-digermadecane]bis(2-methyl-4-phenylindenyldibutylzirconium);

(1-methyl-3-tert-butylcyclopentadienyl)(1-phenyl-4-methoxy-7-chlorofluorenyl)dibutylzirconium;

(4,7-dichloroindenyl)(3,6-dimesitylfluorenyl)dibutylzirconium;

bis(2,7-di-tert-butyl-9-cyclohexylfluorenyl)dibutylzirconium;

(2,7-dimethylfluorenyl)[2,7-bis(1-naphthyl)fluorenyl]dibutylzirconium;

dimethylsilylbis(fluorenyl)dibutylzirconium;

dibutylstannylbis(2-methylfluorenyl)dibutylzirconium;

1,1,2,2-tetraethyldisilanediyl(2-methylindenyl)(4-phenylfluorenyl)dibutylzirconium;

propylene-1-(2-indenyl)-2-(9-fluorenyl)dibutylzirconium;

1,1-dimethyl-1-silaethylenebis(fluorenyl)dibutylzirconium;

[4-(cyclopentadienyl)4,7,7-trimethyl(tetrahydroindenyl)dibutylzirconium;

[4-(cyclopentadienyl)-4,7-dimethyl-7-phenyl(5,6-dimethyl]tetrahydroindenyl]dibutylzirconium;

[4-(cyclopentadienyl)-4,7-dimethyl-7-(1-naphthyl)(7-phenyltetrahydroindenyl)]dibutylzirconium;

[4-(cyclopentadienyl)-4,7-dimethyl-7-butyl(6,6-diethyltetrahydroindenyl)]dibutylzirconium;

[4-(3-tert-butylcyclopentadienyl)-4,7,7-trimethyl(tetrahydroindenyl)]dibutylzirconium;

[4-(1-indenyl)-4,7,7-trimethyl(tetrahydroindenyl)]dibutylzirconium;

bis(cyclopentadienyl)dibutylhafnium;

bis(indenyl)dibutylvanadium;

bis(fluorenyl)dibutylscandium;

(indenyl)(fluorenyl)dibutylniobium;

(2-methyl-7-naphthylindenyl)(2,6-di-tert-butylfluorenyl)dibutyltitanium;

(pentamethylcyclopentadienyl)(tetrahydroindenyl)butylhafnium bromide;

(cyclopentadienyl)(1-octene-8-ylcyclopentadienyl)dibutylhafnium;

(indenyl)(2-butene-4-ylcyclopentadienyl)dibutyltitanium;

[1,3-bis(trimethylsilyl)cyclopentadienyl](3,4-penzofluorenyl)dibutylniobium;

bis(cyclopentadienyl)dibutyltitanium;

dimethylsilanediylbis(indenyl)dibutyltitanium;

dimethylsilanediylbis(tetrahydroindenyl)dibutylhafnium;

dimethylsilanediyl(cyclopentadienyl)(indenyl)dibutyltitanium;

dimethylsilanediylbis(2-methylindenyl)dibutylhafnium;

dimethylsilanediylbis(2-ethylindenyl)methylscandium;

dimethylsilanediylbis(2-butyl-4,5-benzindenyl)dibutylniobium;

dimethylsilanediylbis(2-ethyl-4,5-benzindenyl)dibutyltitanium;

dimethylsilanediylbis(4,5-dihydro-8-methyl-7H-cyclopent[e]acenaphthylene-7-ylidene)dibutyltitanium;

dimethylsilanediyl(2-methyl-4,5-benzindenyl)(2-methyl-4-phenylindenyl)dibutyltitanium;

dimethylsilanediyl(2-ethyl-4,5-benzindenyl)(2-methyl-4-phenylindenyl)dibutylhafnium;

dimethylsilanediyl(2-ethyl-4,5-benzindenyl)(2-ethyl-4-phenylindenyl)methylscandium;

dimethylsilanediyl(2-ethyl-4,5-benzindenyl)(2-ethyl-4-naphthylindenyl)dibutyltitanium;

dimethylsilanediyl(2-methylindenyl)(4-phenylindenyl)dibutylhafnium;

dimethylsilanediylbis(2-methyl-4-phenylindenyl)dibutylniobium;

dimethylsilanediylbis(2-ethyl-4-phenylindenyl)dibutylvanadium;

dimethylsilanediylbis(2-methyl-4,6-diisopropylindenyl)dibutylhafnium;

dimethylsilanediylbis(2-methyl-4,6-diisopropylindenyl)dibutylvanadium;

dimethylsilanediylbis(2-methyl-4-naphthylindenyl)butylhafnium bromide;

dimethylsilanediylbis(2-ethyl-4-naphthylindenyl)dibutyltitanium;

methylphenylsilanediylbis(indenyl)dibutyltitanium;

methylphenylsilanediyl(cyclopentadienyl)(indenyl)hafnium;

methylphenylsilanediylbis(tetrahydroindenyl)dibutylhafnium;

methylphenylsilanediylbis(2-methylindenyl)dibutyltitanium;

methylphenylsilanediylbis(2-ethylindenyl)dibutylhafnium;

methylphenylsilanediylbis(2-methyl-4,5-benzindenyl)dibutylhafnium;

methylphenylsilanediylbis(2-ethyl-4,5-benzindenyl)dibutylvanadium;

methylphenylsilanediylbis(4,5-dihydro-8-methyl-7H-cyclopent[e]acenaphthylene-7-ylidene)dibutyltitanium;

methylphenylsilanediylbis(2-methyl-4,5-benzindenyl)(2-methyl-4-phenylindenyl)butyltitaniumbromide;

methylphenylsilanediylbis(2-ethyl-4,5-benzindenyl)(2-methyl-4-phenylindenyl)dibutyltitanium;

methylphenylsilanediylbis(2-methyl-4,5-benzindenyl)(2-ethyl-4-phenylindenyl)dibutylhafnium;

methylphenylsilanediylbis(2-ethyl-4,5-benzindenyl)(2-ethyl-4-phenylindenyl)dibutylhafnium;

methylphenylsilanediyl(2-methylindenyl)(4-phenylindenyl)dibutyltitanium;

methylphenylsilanediylbis(2-methyl-4-phenylindenyl)dibutylhafnium;

methylphenylsilanediylbis(2-ethyl-4-phenylindenyl)dibutylvanadium;

methylphenylsilanediylbis(2-methyl-4,6-diisopropylindenyl)dibutyltitanium;

methylphenylsilanediylbis(2-ethyl-4,6-diisopropylindenyl)dibutylhafnium;

methylphenylsilanediylbis(2-methyl-4-naphthylindenyl)dibutylhafnium;

methylphenylsilanediylbis(2-ethyl-4-naphthylindenyl)dibutyltitanium;

diphenylsilanediylbis(indenyl)dibutyltitanium;

diphenylsilanediylbis(2-methylindenyl)dibutylhafnium;

diphenylsilanediylbis(2-ethylindenyl)dibutyltitanium;

diphenylsilanediylbis(cyclopentadienyl)(indenyl)dibutylhafnium;

diphenylsilanediylbis(2-methyl-4,5-benzindenyl)dibutyltitanium;

diphenylsilanediylbis(2-ethyl-4,5-benzindenyl)dibutylhafnium;

diphenylsilanediyl(2-methyl-4,5-benzindenyl)(2-methyl-4,5-phenylindenyl)dibutylhafnium;

diphenylsilanediyl(2-ethyl-4,5-benzindenyl)(2-methyl-4,5-phenylindenyl)dibutyltitanium;

diphenylsilanediyl(2-methyl-4,5-benzindenyl)(2-ethyl-4,5-phenylindenyl)dibutylhafnium;

diphenylsilanediyl(2-ethyl-4,5-benzindenyl)(2-ethyl-4,5-phenylindenyl)dibutyltitanium;

diphenylsilanediyl(2-methylindenyl)(4-phenylindenyl)dibutyltitanium;

diphenylsilanediylbis(2-methyl-4-phenylindenyl)dibutyltitanium;

diphenylsilanediylbis(2-ethyl-4-phenylindenyl)dibutylhafnium;

diphenylsilanediylbis(2-methyl-4,6-diisopropylindenyl)dibutylhafnium;

diphenylsilanediylbis(2-ethyl-4,6-diisopropylindenyl)dibutylhafnium;

diphenylsilanediylbis(2-methyl-4-naphthylindenyl)dibutylhafnium;

diphenylsilanediylbis(2-ethyl-4-naphthylindenyl)dibutyltitanium;

1-silacyclopentane-1,1-bis(indenyl)dibutylhafnium;

1-silacyclopentane-1,1-bis(2-methylindenyl)dibutylhafnium;

1-silacyclopentane-1,1-bis(2-ethylindenyl)dibutylhafnium;

1-silacyclopentane-1,1-bis(2-methyl-4,5-benzindenyl)dibutyltitanium;

1-silacyclopentane-1,1-bis(2-ethyl-4,5-benzindenyl)dibutylhafnium;

1-silacyclopentane-1-(2-methyl-4,5-benzindenyl)-1-(2-methyl-4-phenylindenyl)methylscandium;

1-silacyclopentane-1-(2-ethyl-4,5-benzindenyl)-1-(2-methyl-4-phenylindenyl)dibutylhafnium;

1-silacyclopentane-1-(2-methyl-4,5-benzindenyl)-1-(2-ethyl-4-phenylindenyl)dibutyltitanium;

1-silacyclopentane-1-(2-ethyl-4,5-benzindenyl)-1-(2-ethyl-4-phenylindenyl)dibutylhafnium;

1-silacyclopentane-1-(2-methylindenyl)-1-(4-phenylindenyl)dibutylhafnium;

1-silacyclopentane-1,1-bis(2-methyl-4-phenylindenyl)dibutylhafnium;

1-silacyclopentane-1,1-bis(2-ethyl-4-phenylindenyl)dibutyltitaniumbromide;

1-silacyclopentane-1,1-bis(2-methyl-4,6-diisopropylindenyl)dibutyltitanium;

1-silacyclopentane-1,1-bis(2-ethyl-4,6-diisopropylindenyl)dibutyltitanium;

1-silacyclopentane-1,1-bis(2-methyl-4-naphthylindenyl)methylscandium;

1-silacyclopentane-1,1-bis(2-ethyl-4-naphthylindenyl)dibutylhafnium;

bis(cyclopentadienyl)dibutyltitanium;

ethylene-1,2-bis(indenyl)methylscandium;

ethylene-1,2-bis(tetrahydroindenyl)dibutyltitanium;

ethylene-1-(cyclopentadienyl)-2-(1-indenyl)dibutylhafnium;

ethylene-1-(cyclopentadienyl)-2-(2-indenyl)butyltitanium bromide;

ethylene-1-(cyclopentadienyl)-2-(2-methyl-1-indenyl)dibutylhafnium;

ethylene-1,2-bis(2-methylindenyl)dibutylhafnium;

ethylene-1,2-bis(2-ethylindenyl)dibutylhafnium;

ethylene-1,2-bis(2-methyl-4,5-benzindenyl)dibutylhafnium;

ethylene-1,2-bis(2-ethyl-4,5-benzindenyl)dibutyltitanium;

ethylene-1,2-bis(4,5-dihydro-8-methyl-7H-cyclopent[e]acenaphthylene-7-ylidene)dibutyltitanium;

ethylene-1-(2-methyl-4,5-benzindenyl)-2-(2-methyl-4-phenylindenyl)dibutyltitanium;

ethylene-1-(2-ethyl-4,5-benzindenyl)-2-(2-methyl-4-phenylindenyl)dibutyltitanium;

ethylene-1-(2-methyl-4,5-benzindenyl)-2-(2-ethyl-4-phenylindenyl)methylscandium;

ethylene-1-(2-ethyl-4,5-benzindenyl)-2-(2-ethyl-4-naphthylindenyl)dibutylhafnium;

ethylene-1-(2-methylindenyl)-2-(4-phenylindenyl)dibutyltitanium;

ethylene-1,2-bis(2-methyl-4-phenylindenyl)dibutylhafnium;

ethylene-1,2-bis(2-ethyl-4-phenylindenyl)dibutylhafnium;

ethylene-1,2-bis(2-methyl-4,6-diisopropylindenyl)dibutylhafnium;

ethylene-1,2-bis(2-ethyl-4,6-diisopropylindenyl)dibutyltitanium;

ethylene-1,2-bis(2-methyl-4-naphthylindenyl)dibutyltitanium;

ethylene-1,2-bis(2-ethyl-4-naphthylindenyl)dibutylhafnium;

propylene-2,2-bis(indenyl)dibutylhafnium;

propylene-2-cyclopentadienyl-2-(1-indenyl)dibutyltitanium;

propylene-2-cyclopentadienyl-2-(4-phenyl-1-indenyl)dibutyltitanium;

propylene-2-cyclopentadienyl-2-(9-fluorenyl)dibutylhafnium;

propylene-2-cyclopentadienyl-2-(2,7-dimethoxy-9-fluorenyl)dibutylhafnium;

propylene-2-cyclopentadienyl-2-(2,7-di-tert-butyl-9-fluorenyl)dibutylhafnium;

propylene-2-cyclopentadienyl-2-(2,7-dibromo-9-fluorenyl)dibutyltitanium;

propylene-2-cyclopentadienyl-2-(2,7-diphenyl-9-fluorenyl)dibutylhafnium;

propylene-2-cyclopentadienyl-2-(2,7-dimethyl-9-fluorenyl)dibutyltitanium;

propylene-2-(3-methylcyclopentadienyl)-2-(2,7-dibutyl-9-fluorenyl)dibutylhafnium;

propylene-2-(3-tert-butylcyclopentadienyl)-2-(2,7-dibutyl-9-fluorenyl)dibutyltitanium;

propylene-2-(3-trimethylsilylcyclopentadienyl)-2-(3,6-di-tert-butyl-9-fluorenyl)dibutyltitanium;

propylene-2-cyclopentadienyl-2-[2,7-bis(3-butene-1-yl)-9-fluorenyl]dibutylhafnium;

propylene-2-cyclopentadienyl-2-(3-tert-butyl-9-fluoreny-1)dibutyltitanium;

propylene-2,2-bis(tetrahydroindenyl)dibutylhafnium;

propylene-2,2-bis(2-methylindenyl)dibutylhafnium;

propylene-2,2-bis(2-ethylindenyl)dibutyltitanium;

propylene-2,2-bis(2-methyl-4,5-benzindenyl)dibutyltitanium;

propylene-2,2-bis(2-ethyl-4,5-benzindenyl)dibutylhafnium;

propylene-2,2-bis(4,5-dihydro-8-methyl-7H-cyclopent[e]acenaphthylene-7-ylidene)dibutylhafnium;

propylene-2-(2-methyl-4,5-benzindenyl)-2-(2-methyl-4-phenylindenyl)dibutylhafnium;

propylene-2-(2-ethyl-4,5-benzindenyl)-2-(2-methyl-4-phenylindenyl)dibutyltitanium;

propylene-2-(2-methyl-4,5-benzindenyl)-2-(2-ethyl-4-phenylindenyl)dibutylhafnium;

propylene-2-(2-ethyl-4,5-benzindenyl)-2-(2-ethyl-4-naphthylindenyl)dibutyltitanium;

propylene-2-(2-methylindenyl)-2-(4-phenylindenyl)dibutylhafnium;

propylene-2,2-bis(2-methyl-4-phenylindenyl)dibutyltitanium;

propylene-2,2-bis(2-ethyl-4-phenylindenyl)dibutylhafnium;

propylene-2,2-bis(2-methyl-4,6-diisopropylindenyl)dibutyltitanium;

propylene-2,2-bis(2-ethyl-4,6-diisopropylindenyl)dibutylhafnium;

propylene-2,2-bis(2-methyl-4-naphthylindenyl)dibutyltitanium;

propylene-2,2-bis(2-ethyl-4-naphthylindenyl)dibutyltitanium;

1,6-bis[methylsilylbis(2-methyl-4-phenylindenyl)dibutylhafnium]hexane;

1,6-bis[methylsilylbis(2-methyl-4,5-benzindenyl)dibutyltitanium]hexane;

1,6-bis[methylsilylbis(2-ethyl-4-phenylindenyl)dibutylhafnium]hexane;

1,6-bis[methylsilylbis(2-methyl-4-naphthylindenyl)dibutyltitanium]hexane;

1,6-bis[methylsilylbis(2-methyl-4,6-diisopropylindenyl)dibutylhafnium]hexane;1,6-bis[methylsilyl(2-methyl-4-phenylindenyl)(4,5-benzindenyl)dibutyltitanium]hexane;

1-[methylsilylbis(tetrahydroindenyl)dibutylhafnium]-6-[ethylstannyl(cyclopentadienyl)(fluorenyl)dibutyltitanium]hexane;

1,6-disila-1,1,6,6-tetramethyl-1,6-bis[methylsilylbis(2-methyl-4-phenylindenyl)dibutylhafnium]hexane;

1,4-disila-1,4-bis[methylsilylbis(2-methyl-4-phenylindenyl)dibutylhafnium]cyclohexane;

[1,4-bis(1-indenyl)-1,1,4,4-tetramethyl-1,4-disilabutane]bis(pentamethylcyclopentadienyldibutylhafnium);

[1,4-bis(9-fluorenyl)-1,1,4,4-tetramethyl-1,4-disilabutane]bis(cyclopentadienyldibutylhafnium);

[1,4-bis(1-indenyl)-1,1,4,4-tetramethyl-1,4-disilabutane]bis(cyclopentadienyldibutyltitanium);

[1-(1-indenyl)-6-(2-phenyl-1-indenyl)-1,1,6,6-tetraethyl-1,6-disila-4-oxahexane]bis(tert-butylcyclopentadienyldibutyltitanium);

[1,10-bis(2,3-dimethyl-1-indenyl)-1,1,10,10-tetramethyl-1,10-digermadecane]bis(2-methyl-4-phenylindenyldibutylhafnium);

(1-methyl-3-tert-butylcyclopentadienyl)(1-phenyl-4-methoxy-7-chlorofluorenyl)dibutyltitanium;

(4,7-dichloroindenyl)(3,6-dimesitylfluorenyl)dibutyltitanium;

bis(2,7-di-tert-butyl-9-cyclohexylfluorenyl)dibutylhafnium;

(2,7-dimesitylfluorenyl)[2,7-bis(1-naphthyl)fluorenyl]dibutylhafnium;

dimethylsilylbis(fluorenyl)dibutyltitanium;

dibutylstannylbis(2-methylfluorenyl)dibutylhafnium;

1,1,2,2-tetraethyldisilanediyl(2-methylindenyl)(4-phenylfluorenyl)dibutyltitanium;

propylene-1-(2-indenyl)-2-(9-fluorenyl)dibutylhafnium;

1,1-dimethyl-1-silaethylenebis(fluorenyl)dibutyltitanium;

[4-(cyclopentadienyl)4,7,7-trimethyl(tetrahydroindenyl]dibutyltitanium;

[4-(cyclopentadienyl)4,7-dimethyl-7-phenyl(5,6-dimethyltetrahydroindenyl]dibutylhafnium;

[4-(cyclopentadienyl)-4,7-dimethyl-7-(1-naphthyl)(7-phenyltetrahydroindenyl]dibutyltitanium;

[4-(cyclopentadienyl)-4,7-dimethyl-7-butyl(6.6-diethyltetrahydroindenyl)]dibutylhafnium;

[4-(3-tert-butylcyclopentadienyl)-4,7,7-trimethyl(tetrahydroindenyl)]dibutylhafnium;

[4-(1-indenyl)-4,7,7-trimethyl(tetrahydroindenyl)]dibutyltitanium;

bis(cyclopentadienyl)dibutylhafnium;

bis(cyclopentadienyl)dichlorozirconium;

bis(indenyl)dichlorozirconium;

bis(fluorenyl)dichlorozirconium;

(indenyl)(fluorenyl)dichlorozirconium;

bis(cyclopentadienyl)dichlorotitanium;

(dimethylsilanediyl)bis(indenyl)dichlorozirconium;

(dimethylsilanediyl)bis(tetrahydroindenyl)dichlorozirconium;

(dimethylsilanediyl)(indenyl)dichlorozirconium;

(dimethylsilanediyl)bis(2-methylindenyl)dichlorozirconium;

(dimethylsilanediyl)bis(2-ethylindenyl)dichlorozirconium;

(dimethylsilanediyl)bis(2-methyl-4,5-benzindenyl)dichlorozirconium;

(dimethylsilanediyl)bis(2-ethyl-4,5-benzindenyl)dichlorozirconium;

(dimethylsilanediyl)bis(2-methyl-4-phenylindenyl)dichlorozirconium;

(dimethylsilanediyl)bis(2-ethyl-4-phenylindenyl)dichlorozirconium;

(dimethylsilanediyl)bis(2-methyl-4,6-diisopropylindenyl)dichlorozirconium;

bis(cyclopentadienyl)(η₄-butadiene)zirconium;

bis(methylcyclopentadienyl)(η₄-butadiene)zirconium;

bis(n-butylcyclopentadienyl)(η₄-butadiene)zirconium;

bisindenyl(η₄-butadiene)zirconium;

(tert-butylamido)dimethyl(tetramethyl-η₅-cyclopentadienyl)silane(η₄-butadiene)zirconium;

bis(2-methylbenzindenyl)(η₄-butadiene)zirconium;

dimethylsilanediylbis(2-methyl-indenyl)(η₄-butadiene)zirconium;

dimethylsilanediylbisindenyl(η₄-butadiene)zirconium;

dimethylsilanediylbis(2-methylindenyl)(η₄-butadiene)zirconium;

dimethylsilanediyl(2-methylbenzindenyl)(2-methyl-indenyl)(η₄-butadiene)zirconium;

dimethylsilanediyl(2-methylbenzindenyl)(2-methyl-4-phenylindenyl)(η₄-butadiene)zirconium;

dimethylsilanediyl(2-methylindenyl)(4-phenylindenyl)(η₄-butadiene)zirconium;

dimethylsilanediylbis(2-methyl-4-phenylindenyl)(η₄-butadiene)zirconium;

dimethylsilanediylbis(2-methyl-4,6-diisopropylindenyl)(η₄-butadiene)zirconium;

dimethylsilanediylbis(2-methyl-4-naphthylindenyl)(η₄-butadiene)zirconium;

isopropylidene(cyclopentadienyl)(fluorenyl)(η₄-butadiene)zirconium;

isopropylidene(cyclopentadienyl)(indenyl)(η₄-butadiene)zirconium;

(4-η₅-cyclopentadienyl)-4,7,7-trimethyl-(η_(5,4,5,6,7)-tetrahydroindenyl)(η₄-butadiene)zirconium;

dimethylsilanediylbis(2-methyl-indenyl)(η₄-butadiene)zirconium;

dimethylsilanediylbisindenyl(η₄-butadiene)zirconium;

dimethylsilanediylbis(2-methylbenzindenyl)(η₄-butadienezirconium;

dimethylsilanediyl(2-methylbenzindenyl)(2-methyl-indenyl)(η₄-butadiene)zirconium;

dimethylsilanediyl(2-methylbenzindenyl)(2-methyl-4-phenylindenyl)(η₄-butadiene)zirconium;

dimethylsilanediyl(2-methylindenyl)(4-phenylindenyl)(η₄-butadiene)zirconium;

dimethylsilanediylbis(2-methyl-4-phenylindenyl)(η₄-butadiene)zirconium;

dimethylsilanediylbis(2-methyl-4,6-diisopropylindenyl)(η₄-butadiene)zirconium;

dimethylsilanediylbis(2-methylindenyl)(η₄-butadiene)zirconium;

dimethylsilanediylbisindenyl(η₄-butadiene)zirconium;

dimethylsilanediylbis(2-methylbenzindenyl)(η₄-butadiene)zirconium;

dimethylsilanediyl(2-methylbenzindenyl)(2-methylindenyl)(η₄-butadiene)zirconium;

dimethylsilanediyl(2-methylbenzindenyl)(2-methyl-4-phenylindenyl)(η₄-butadiene)zirconium;

dimethylsilanediyl(2-benzindenyl)(4-phenylindenyl)(η₄-butadiene)zirconium;

dimethylsilanediylbis(2-methyl-4-phenylindenyl)(η₄-butadiene)zirconium;

dimethylsilanediylbis(2-methyl-4,6-diisopropylindenyl)(η₄-butadiene)zirconium;

dimethylsilanediylbis(2-methyl-4-naphthylindenyl)(η₄-butadiene)zirconium;

dimethylsilanediylbis(2-methylindenyl)(η₄-butadiene)zirconium;

dimethylsilanediylbisindenyl(η₄-butadiene)zirconium;

dimethylsilanediylbis(2-methylbenzindenyl)(η₄-butadiene)zirconium;

dimethylsilanediyl(2-methylbenzindenyl)(2-methylindenyl)(η₄-butadiene)zirconium;

dimethylsilanediyl(2-methylbenzindenyl)(2-methyl-4-phenylindenyl)(η₄-butadiene)zirconium;

dimethylsilanediyl(2-methylbenzindenyl)(4-phenylindenyl)(η₄-butadiene)zirconium;

dimethylsilanediylbis(2-methyl-4-phenylindenyl)(η₄-butadiene)zirconium;

dimethylsilanediylbis(2-methyl-4,6-diisopropylindenyl)(η₄-butadiene)zirconium;

dimethylsilanediylbis(2-methyl-4-naphthylindenyl)(η₄-butadiene)zirconium;

methylphenylmethylene(fluorenyl)(cyclopentadienyl)(η₄-butadiene)zirconium;

diphenylmethylene(fluorenyl)(cyclopentadienyl)(η₄-butadiene)zirconium;

isopropylidene(3-methylcyclopentadienyl)(fluorenyl)(η₄-butadiene)zirconium;

dimethylsilanediyl(3-tert-butylcyclopentadienyl)(fluorenyl)(η₄-butadiene)zirconium;

diphenylsilanediyl(3-(trimethylsilyl)cyclopentadienyl)(fluorenyl)(η₄-butadiene)zirconium;

phenylmethylsilanediylbis(2-methylindenyl)(η₄-butadiene)zirconium;

phenylmethylsilanediylbisindenyl(η₄-butadiene)zirconium;

phenylmethylsilanediylbis(2-methyl-4,5-benzindenyl)(η₄-butadiene)zirconium;

phenylmethylsilanediyl(2-methyl-4,5-benzindenyl)(2-methylindenyl)(η₄-butadiene)zirconium;

phenylmethylsilanediyl(2-methyl-4,5-benzindenyl)(2-methyl-4-phenylindenyl)(η₄-butadiene)zirconium;phenylmethylsilanediyl(2-methylindenyl)(4-phenylindenyl)(η₄-butadiene)zirconium;

phenylmethylsilanediylbis(2-methyl-4-phenylindenyl)(η₄-butadiene)zirconium;

phenylmethylsilanediylbis(2-ethyl-4-phenylindenyl)(η₄-butadiene)zirconium;

phenylmethylsilanediylbis(2-methyl-4,6-diisopropylindenyl)(η₄-butadiene)zirconium;

phenylmethylsilanediylbis(2-methyl-4-naphthylindenyl)(η₄-butadiene)zirconium;

ethylenebis(2-methylindenyl)(η₄-butadiene)zirconium;

ethylenebisindenyl(η₄-butadiene)zirconium;

ethylenebis(2-methyl-4,5-benzindenyl)(η₄-butadiene)zirconium;

ethylene(2-methyl-4,5-benzindenyl)(2-methyl-4-phenylindenyl)(η₄-butadiene)zirconium;

ethylene(2-methylindenyl)(2-methyl-4-phenylindenyl)(η₄-butadiene)zirconium;

ethylene(2-methylindenyl)(4-phenyl-indenyl)(η₄-butadiene)zirconium;

ethylenebis(2-methyl-4,5-benzindenyl)(η₄-butadiene)zirconium;

ethylenebis(2-methyl-4-phenylindenyl)(η₄-butadiene)zirconium;

ethylenebis(2-methyl-4,6-diisopropylindenyl)(η₄-butadiene)zirconium;

ethylenebis(2-methyl-4-naphthylindenyl)(η₄-butadiene)zirconium;

ethylenebis(2-ethyl-4-phenylindenyl)(η₄-butadiene)zirconium;

ethylenebis(2-ethyl-4,6-diisopropylindenyl)(η₄-butadiene)zirconium;

ethylenebis(2-ethyl-4-naphthylindenyl)(η₄-butadiene)zirconium;

dimethylsilanediylbis(2-ethyl-4-phenylindenyl)(η₄-butadiene)zirconium;

dimethylsilanediylbis(2,3,5-trimethylcyclopentadienyl)(η₄-butadiene)zirconium;

1,6-{bis[methylsilylbis(2-methyl-4-phenylindenyl(η₄-butadiene)zirconium]}hexane;

1,6-{bis[methylsilylbis(2-ethyl-4-phenylindenyl(η₄-butadiene)zirconium]}hexane;

1,6-{bis[methylsilylbis(2-methyl-4-naphthylindenyl(η₄-butadiene)zirconium]}hexane;

1,6-{bis[methylsilylbis(2-methyl-4,5-benzindenyl(η₄-butadiene)zirconium]}hexane;

1,6-{bis[methylsilyl(2-methyl-4-phenylindenyl)(2-methylindenyl(η₄-butadiene)zirconium]}hexane;

1,2-{bis[methylsilylbis(2-methyl-4-phenylindenyl(η₄-butadiene)zirconium]}ethane;

1,2-{bis[methylsilylbis(2-ethyl-4-phenylindenyl(η₄-butadiene)zirconium]}ethane;

1,2-{bis[methylsilylbis(2-methyl-4-naphthylindenyl(η₄-butadiene)zirconium]}ethane;

1,2-{bis[methylsilylbis(2-methyl-4,5-benzindenyl(η₄-butadiene)zirconium)]}ethane;and,

1,2-{bis[methylsilyl(2-methyl-4-phenylindenyl)(2-methylindenyl)(η₄-butadiene)zirconium]}ethane.

EXAMPLES

Hereinafter the present invention will be described with reference toEXAMPLES below but is not deemed to be limited thereto.

The following reaction was carried out in an argon or nitrogenatmosphere using the standard Schlenk technique. Solvents were providefor use after they were dried by refluxing in the presence of anappropriate drying agent and then distilling in an argon or nitrogenflow.

In the following EXAMPLES, the number average molecular weight (Mn) ofpolymers was determined by gel permeation chromatography, while theweight average molecular weight (Mw) was determined by elementalanalysis.

Reference Example 1 Synthesis of 1,8-bis(p-Bromophenyl)-1,7-octadiyne

p-Bromoiodobenzene (10 ml), 1,7-octadiyne, Pd(PPh₃)₄ (0.05 mmol), Cul(0.1 mmol) and tetrahydrofuran (hereinafter abbreviated as THF, 30 ml)were mixed in a Schlenk tube to give a solution. Triethylamine was addedto the solution. The mixture was stirred at room temperature for 48hours to proceed the reaction. The reaction was quenched with 3Nhydrochloric acid. Next, the organic phase was extracted with diethylether followed by drying over anhydrous magnesium sulfate. The solventwas removed in vacuum to give a solid. The solid was washed with hexaneto give the yellowish green solid in 75% yield.

¹H NMR (CDCl₃, Me₄Si) δ 1.75-1.78 (m, 4H), 2.44-2.47 (m, 4H), 7.23-7.26(m, 4H), 7.39-7.42 (m, 4H); ¹³C NMR (CDCl₃, Me₄Si) δ 19.01 (2C), 27.73(2C), 79.98 (2C), 91.00 (2C), 121.65 (2C), 122.86 (2C), 131.40 (4C),132.99 (4C).

Example 12,5-bis(p-Bromophenyl)-cyclohexa[c]-1-zirconacyclopenta-2,4-diene

Bis-η⁵-cylopentadienyl)dibutylzirconium (1.2 mmol) and THF (10 ml) werecharged in a Schlenk tube. The solution was cooled to −78° C. and thenn-butyl lithium (2.4 mmol) was added to the solution. The solution wasallowed to stir at −78° C. for an hour. After1,8-bis(p-bromophenyl)-1,7-octadiyne (1.0 mmol) was added to thereaction mixture at −78° C., the mixture was warmed to room temperaturefor an hour to give the title compound.

Example 21,4-bis(p-Bromophenyl)-2,3-dimethoxycarbonyl-5,6,7,8-tetrahydronaphthalene

2,5-Bis(p-bromophenyl)-cyclohexa[c]-1-zirconacyclopenta-2,4-dieneobtained in EXAMPLE 1 was used in the solution state, without separatingthe diene. That is, dimethylacetylene dicarboxylate (TCI Inc., 2.5 mmol)and copper (I) chloride (2.5 mmol) were added at 0° C. to a THF (10 ml)solution of2,5-bis(p-bromophenyl)-cyclohexa[c]-1-zirconacyclopenta-2,4-diene (1.0mmol). The reaction mixture was warmed to room temperature followed bystirring for 6 hours. The reaction was quenched with 3N hydrochloricacid. Next, extraction was conducted with ether followed by drying overanhydrous magnesium sulfate. Column chromatography (hexane:diethylether=4:1) on silica gel gave the title compound in 80% yield.

¹H NMR (CDCl₃, Me₄Si) δ 1.64-1.65 (m, 4H), 2.40-2.42 (m, 4H), 3.47 (s,6H), 7.08-7.10 (m, 4H), 7.53-7.55 (m, 4H); ¹³C NMR (CDCl₃, Me₄Si) δ22.32 (2C), 29.06 (2C), 52.12 (2C), 121.65 (2C), 129.72 (2C), 130.69(4C), 131.32 (4C), 137.54 (2C), 138.64 (2C), 138.72 (2C), 168.19 (2C).High resolution mass spectrum (HRMS) for C₂₆H₂₂O₄Br₂: calcd. 555.9883;found 555.9873.

The reactions occurred in REFERENCE EXAMPLE 1 to EXAMPLE 2 aresummarized below.

Example 3Poly(1,4-phenylene-2′,3′-dimethoxycarbonyl-5′,6′,7′,8′-tetrahydronaphthalene-1′,4′-diyl-1″,4″-phenylene)

In a 20 ml Schlenk tube, bistriphenylphosphine dichloronickel (II) (0.05mmol), bipyridine (0.05 mmol), metallic zinc (1.5 mmol) and1,4-bis(p-bromophenyl)-2,3-dimethoxycarbonyl-5,6,7,8-teetrahydronaphthalenewere charged. Next, dry dimethylformamide (5 ml) was added to themixture followed by stirring for 3 hours at 80° C. A large amount of 3Nhydrochloric acid and methanol were added to the resulting mixture toterminate the reaction. The solid in the solution was filtered, washedwith methanol, diethyl ether and methanol, and dried in vacuum at 80° C.for 12 hours. The polymer was obtained as yellowish green solids in 75%yield.

According to gel permeation chromatography, the number average molecularweight (Mn) was 6870 and Mw/Mn was 1.7.

When the reaction was carried out at 80° C. for 24 hours instead of thereaction at 80° C. for 3 hours, the number average molecular weight (Mn)was 7510 and Mw/Mn was 1.8, according to gel permeation chromatography.

Example 42,5-bis(p-Bromophenyl)-cyclopenta[c]-1-zirconacyclopenta-2,4-diene

Bis(η⁵-cyclopentadienyl)dibutylzirconium (1.2 mmol) and THF (10 ml) werecharged in a Schlenk tube. The solution was cooled to −78° C. and thenn-butyl lithium (2.4 mmol) was added to the solution. The solution wasallowed to stir at −78° C. for an hour. After1,7-bis(p-bromophenyl)-1,6-heptadiyne (1.0 mmol) was added to thereaction mixture at −78° C., the resulting mixture was warmed to roomtemperature for an hour to give the title compound.

Example 5 4,7-bis(p-Bromophenyl)-5,6-dimethoxycarbonylindan

To a solution of2,5-bis(p-bromophenyl)-cyclopenta[c]-1-zirconacyclopenta-2,4-diene (1.0mmol) in THF (10 ml), dimethylacetylene dicarboxylate (TCI Inc., 2.5mmol) and bistriphenylphosphine dibromonickel (II), NiBr₂(PPh₃)₂ (2.5mmol) were added at 0° C. The reaction mixture was warmed to roomtemperature followed by stirring for 6 hours. The reaction was quenchedwith 3N hydrochloric acid. Next, extraction was conducted with etherfollowed by drying over anhydrous magnesium sulfate. Columnchromatography (hexane:diethyl ether=4:1) on silica gel gave the titlecompound.

¹H NMR (CDCl₃, Me₄Si) δ 1.96-2.03 (m, 2H), 2.77 (t, J=7.4 Hz, 4H), 3.54(s, 6H), 7.14 (d, J=8.2 Hz, 4H), 7.54 (d, J=8.2 Hz, 4H). ¹³C NMR (CDCl₃,Me₄Si) δ 24.79, 32.93 (2C), 52.20 (2C), 121.70 (2C), 130.12 (4C), 130.78(2C), 131.30 (4C), 135.29 (2C), (2C), 137.40 (2C), 145.78 (2C), 168.26(2C). High resolution mass spectrum (HRMS) for C₂₅H₂₀O₄Br₂:

calcd.: C, 55.17; H, 3.70; Br, 29.36 found: C, 55.34; H, 3.89; Br, 29.07

Example 6Poly(1,4-phenylene-5′,6′-dimethoxycarbonylindan-4′,7′-diyl-1″,4″-phenylene)

Next, bistriphenylphosphine dichloronickel (II) (0.05 mmol), bipyridine(0.05 mmol), metallic zinc (1.5 mmol) and teraryl were charged in a 20ml Schlenk tube, obtained in EXAMPLE 5. Next, dry dimethylformamide (5ml) was added to the mixture followed by stirring for 3 hours or 24hours at 80° C. A large amount of 3N hydrochloric acid and methanol wereadded to the resulting mixture to terminate the reaction. The solid inthe solution was filtered, washed with methanol, diethyl ether andmethanol, and dried in vacuum at 80° C. for 12 hours to give thepolyarylene in 48% yield.

The results are shown in TABLE 1.

TABLE 1 Yield (%) Mn Mw Mw/Mn 3 hours 82 4750 5750 1.2 24 hours 85 48105850 1.2

Example 72,5-bis(p-Bromophenyl)-cyclofurana[c]-1-zirconacyclopenta-2,4-diene

Bis(η⁵-cyclopentadienyl)dibutylzirconium (1.2 mmol) and THF (10 ml) werecharged in a Schlenk tube. The solution was cooled to −78° C. and thenn-butyl lithium (2.4 mmol) was added to the solution. The solution wasstirred at −78° C. for an hour. After1,7-bis(p-bromophenyl)-4-oxa-1,6-heptadiyne, namely,di(3-(p-bromophenyl)-2-propynyl) ether (1.0 mmol) was added to thereaction mixture at −78° C., the mixture was warmed to room temperaturefor an hour to give the title compound.

That is, the title compound is one of the compounds represented byformula (V) described above, in which R¹ and R² are combined together toform a group shown by formula: —CH₂—CH₂—O—CH₂—CH₂—, and the 5-memberedring intervened by the oxygen atom is condensed withzirconacyclopentadiene.

Example 84,7-Bis(p-Bromophenyl)-5,6-dimethoxycarbonyl-1,3-dihydroisobenzofuran

To a solution of the compound obtained in EXAMPLE 7 in THF (10 ml),dimethylacetylene dicarboxylate (TCI Inc., 2.5 mmol),bistriphenylphosphine dibromonickel (II) and NiBr₂(PPh₃ ₂ (2.5 mmol)were added at 0° C. The reaction mixture was warmed to room temperaturefollowed by stirring for 12 hours. The reaction was quenched with 3Nhydrochloric acid. Next, extraction was conducted with ether followed bydrying over anhydrous magnesium sulfate. Column chromatography(hexane:diethyl ether=4:1) on silica gel gave the title compound in 65%yield.

¹H NMR (CDCl₃, Me₄Si) δ 3.58 (s, 6H), 4.98 (s, 4H), 7.15 (d, J=8.2 Hz),7.56 (d, J=8.2 Hz). ¹³C NMR (CDCl₃, Me₄Si) δ 52.48(2C), 73.73 (2C),122.52 (2C), 129.59 (4C), 131.77 (4C), 132.28 (2C), 133.17 (2C), 136.06(2C), 140.96 (2C), 167.66 (2C).

Example 9Poly(1,4-phenylene-5′,6′-dimethoxycarbonyl-1′,3′-dihydroisobenzofuran-4′,7′-diyl-1″,4″-phenylene)

In a 20 ml Schlenk tube obtained in EXAMPLE 8, bistriphenylphosphinedichloronickel (II) (0.05 mmol), bipyridine (0.05 mmol), metallic zinc(1.5 mmol) and the teraryl were charged. Next, dry dimethylformamide (5ml) was added to the mixture followed by stirring for 3 hours or 24hours at 80° C. A large amount of 3N hydrochloric acid and methanol wereadded to the resulting mixture to terminate the reaction. The solid inthe solution was filtered, washed with methanol, diethyl ether andmethanol, and dried in vacuum at 80° C. for 12 hours to give thepolyarylene in 74% yield.

The molecular weight was found to be 6700 by elemental analysis.

Example 10

Mixture of

2,4-bis(p-bromophenyl)-3,5-dibutyl-1-zirconacyclopenta-2,4-diene,2,5-bis(p-bromophenyl)-3,4-dibutyl-1-zirconacyclopenta-2,4-diene and3,4-bis(p-bromophenyl)-2,5-dibutyl-1-zirconacyclopenta-2,4-diene:

Bis(η⁵-cyclopentadienyl)dibutylzirconium (1.2 mmol) and THF (10 ml) werecharged in a Schlenk tube. The solution was cooled to −78° C. and thenn-butyl lithium (2.4 mmol) was added to the solution. The solution wasallowed to stir at −78° C. for an hour. After 1-(p-bromophenyl)-1-hexyne(1.0 mmol) was added to the reaction mixture at −78° C., the resultingmixture was warmed to room temperature for an hour to give a mixture of2,4-bis(p-bromophenyl)-3,5-dibutyl-1-zirconacyclopenta-2,4-diene (5parts by weight),2,5-bis(p-bromophenyl)-3,4-dibutyl-1-zirconacyclopenta-2,4-diene (1 partby weight) and3,4-bis(p-bromophenyl)-2,5-dibutyl-1-zirconacyclopenta-2,4-diene (1 partby weight).

In this EXAMPLE, the three isomers of the zirconacyclopenta-2,4-dienederivatives are not separated. However, these derivatives can beseparated from each other by chromatography, if desired, followed byrecrystallization.

Example 11

Mixture of

1,5-bis(p-bromophenyl)-2,3-dimethoxycarbonyl-4,6-dibutylbenzene,

1,4-bis(p-bromophenyl)-2,3-dimethoxycarbonyl-5,6-dibutylbenzene and

1,2-bis(p-bromophenyl)-4,5-dimethoxycarbonyl-3,6-dibutylbenzene.

To a solution of the mixture obtained in EXAMPLE 10 in THF (10 ml),dimethylacetylene dicarboxylate (TCI Inc., 2.5 mmol) and copper (I)chloride (2.5 mmol) were added at 0° C. The reaction mixture was warmedto room temperature followed by stirring for 6 hours. The reaction wasquenched with 3N hydrochloric acid. Next, extraction was performed withether followed by drying over anhydrous magnesium sulfate. Columnchromatography (hexane:diethyl ether=4:1) was performed on silica gelgave the mixture of three kinds of monomers (5:1:1) in 80% yield.

1,5-bis(p-Bromophenyl)-2,3-dimethoxycarbonyl-4,6-dibutylbenzene

¹H NMR (CDCl₃, Me₄Si) δ 0.43 (t, J=7.3 Hz, 3H), 0.69 (t, J=7.4 Hz, 3H),0.75-0.85 (m, 2H), 0.95-1.05 (m, 2H), 1.06-1.20 (m, 2H), 1.25-1.40 (m,2H), 2.00-2.20 (m, 2H), 2.40-2.55 (m, 2H), 3.47 (s, 3H), 3.84 (s, 3H),7.08 (d, J=8.3 Hz, 2H), 7.14 (d, J=8.2 Hz, 2H), 7.50 (d, J=8.4 Hz, 2H),7.57 (d, J=8.2 Hz, 2H). ¹³C NMR (CDCl₃, Me₄Si) δ 12.79, 13.22, 22.26,22.55, 30.56, 30.61, 32.06, 33.08, 51.79, 52.15, 121.23, 121.36, 129.27,130.67 (2C), 130.96 (2C), 130.99 (2C), 131.06 (2C), 132.77, 136.47,137.26, 137.77, 139.32, 142.09, 142.89, 168.14, 168.37.

1,4-bis(p-Bromophenyl)-2,3-dimethoxycarbonyl-5,6-dibutylbenzene

¹H NMR (CDCl₃, Me₄Si) δ 0.66 (t, J=7.2 Hz, 6H), 0.75-0.85 (m, 4H),1.06-1.20 (m, 4H), 2.40-2.50 (m, 4H), 3.44 (s, 6H), 6.81 (d, J=8.2 Hz,4H), 7.27(d, J=8.3 Hz, 4H). ¹³C NMR (CDCl₃, Me₄Si) δ 13.20 (2C), 22.48(2C), 29.62 (2C), 30.45 (2C), 51.70 (2C), 120.63 (2C), 130.20 (2C),130.98 (4C), 131.21 (4C), 137.59 (2C), 142.09 (2C), 142.70 (2C),168.60(2C).

1,2-bis(p-Bromophenyl)-4,5-dimethoxycarbonyl-3,6-dibutylbenzene

¹H NMR (CDCl₃, Me₄Si) δ 0.72 (t, J=7.3 Hz, 6H), 0.96-1.06 (m, 4H),1.25-1.40 (m, 4H), 2.45-2.55 (m, 4H), 3.89 (s, 6H), 7.16 (d, J=8.0 Hz,4H), 7.53 (d, J=8.3 Hz, 4H). ¹³C NMR (CDCl₃, Me₄Si) δ 13.20 (2C), 22.68(2C), 30.38 (2C), 32.72 (2C), 52.1 (2C), 121.41 (2C), 130.49 (4C),130.90 (4C), 131.85 (2C), 136.99 (2C), 138.62 (2C), 142.09 (2C), 168.64(2C). High resolution mass spectrum (HRMS) of the mixture forC₂₆H₂₂O₄Br₂: calcd.: 555.9883; found: 555.9873.

In this EXAMPLE, the three kinds of monomers are not separated. However,these monomers can be separated from each other by chromatography or thelike. In particular,1,5-bis(p-bromophenyl)-2,3-dimethoxycarbonyl-4,6-dibutylbenzene, whichis predominantly formed, can be readily isolated from the other isomers.

Example 12Poly(1,4-phenylene-2′,3′-dimethoxycarbonyl-dibutylphenylene-1″,4″-phenylene)

In a 20 ml Schlenk tube, bistriphenylphosphine dichloronickel (II) (0.05mmol), bipyridine (0.05 mmol), metallic zinc (1.5 mmol) and the mixtureof three kinds of monomers obtained in EXAMPLE 11 were charged. Next,dry dimethylformamide (5 ml) was added to the mixture followed bystirring for 3 hours or 24 hours at 80° C. A large amount of 3Nhydrochloric acid and methanol were added to the resulting mixture toterminate the reaction. The solid in the solution was filtered, washedwith methanol, diethyl ether and methanol, and dried in vacuum at 80° C.for 12 hours. The polymer was obtained as yellowish green solids in 75%yield.

TABLE 2 Yield (%) Mn Mw Mw/Mn 3 hours 78 5370 6760 1.3 24 hours 80 51506480 1.3

Example 13

The reaction was carried out in a manner similar to EXAMPLE 5 to givethe teraryl and, the teraryl was reacted in a manner similar to EXAMPLE6 to give the polyarylene, except that the following acetylenederivatives were used in place of dimethylacetylene dicarboxylate inEXAMPLE 5.

(wherein A¹ and A² are as given in the table below and n is an integerof 2 or more.)

TABLE 3 No. A1 A2 1 Pr Pr 2 Et Et 3 Pr H 4 Ph H 5 EtO H 6 Ph COOEt 7 EtCOMe

The polyarylenes of the present invention find extensive explications aselectrically conductive resins. The polyarylenes can be used also asresin compositions in a variety of formed shapes.

What is claimed is:
 1. A polyarylene comprising a recurring unit offormula (I) or (II) below:

(wherein: Ar¹ and Ar², which may be the same or different, eachrepresents independently an arylene having 4 to 18 carbon atoms, whichmay be substituted and may contain 1 to 5 nitrogen atoms; R¹ and R²,which may be the same or different, each represents independently aC₁-C₂₀ hydrocarbon group which may be substituted, a C₁-C₂₀ alkoxy groupwhich may be substituted, a C₆-C₂₀aryloxy group which may besubstituted, an amine group, hydroxy group or a group shown by formula:—Si(R³)(R⁴)(R⁵) (wherein R³, R⁴ and R⁵, which may be the same ordifferent, each represents independently a C₁-C₂₀ alkyl group, a C₆-C₂₀arylalkyl group, a C₁-C₂₀ alkoxy group or a C₆-C₂₀ arylalkyloxy group);provided that, in the recurring unit of formula (I), R¹ and R² may formtogether a C₄-C₂₀ saturated or unsaturated ring which may be intervenedby an oxygen atom and may be substituted; A¹ and A², which may be thesame or different, each represents independently hydrogen atom; a C₁-C₂₀hydrocarbon group which may be substituted; a C₁-C₂₀ alkoxy group whichmay be substituted; a C₆-C₂₀ aryloxy group which may be substituted; aC₆-C₂₀ alkylaryloxy group which may be substituted; a C₁-C₂₀alkoxycarbonyl group which may be substituted; a C₆-C₂₀ aryloxycarbonylgroup which may be substituted; cyano group (—CN); carbamoyl group(—C(═O)NH₂); a haloformyl group (—C(═O)—X, wherein X is a halogen atom);or formyl group (—C(═O)—H); and, n is an integer of 2 or more).
 2. Thepolyarylene according to claim 1, wherein each of Ar¹ and Ar², which maybe the same or different, represents independently a phenylene groupwhich may be substituted.
 3. The polyarylene according to claim 1, whichhas the recurring unit shown by formula (I), wherein R¹ and R² formtogether a C₄-C₂₀ saturated or unsaturated ring which may be intervenedby an oxygen atom and may be substituted.
 4. The polyarylene accordingto claim 1, wherein the C₁-C₂₀ hydrocarbon group is a linear or branchedC₁-C₂₀ alkyl group, a linear or branched C₂-C₂₀ alkenyl group, a linearor branched C₂-C₂₀ alkynyl group, a linear or branched C₃-C₂₀ allylgroup, a linear or branched C₄-C₂₀ alkadienyl group, a linear orbranched C₄-C₂₀ polyenyl group, a C₆-C₁₈ aryl group, a C₆-C₂₀ alkylarylgroup, a C₆-C₂₀ arylalkyl group, a C₄-C₂₀ cycloalkyl group, or a C₄-C₂₀cycloalkenyl group.
 5. A resin composition comprising the polyaryleneaccording to claim 1 and a synthetic organic polymer.
 6. A terarylrepresented by formula (III) or (IV) below:

(wherein: Ar¹ and Ar², which may be the same or different, eachrepresents independently an arylene having 4 to 18 carbon atoms, whichmay be substituted and may contain 1 to 5 nitrogen atoms; R¹ and R²,which may be the same or different, each represents independently aC₁-C₂₀ hydrocarbon group which may be substituted, a C₁-C₂₀ alkoxy groupwhich may be substituted, a C₆-C₂₀ aryloxy group which may besubstituted, an amine group, hydroxy group or a group shown by formula:—Si(R³)(R⁴)(R⁵) (wherein R³, R⁴ and R⁵, which may be the same ordifferent, each represents independently a C₁-C₂₀ alkyl group, a C₆-C₂₀arylalkyl group, a C₁-C₂₀ alkoxy group or a C₆-C₂₀ arylalkyloxy group)provided that, in the recurring unit of formula (III), R¹ and R² mayform together a C₄-C₂₀ saturated or unsaturated ring which may beintervened by an oxygen atom and may be substituted; A¹ and A², whichmay be the same or different, each represents independently hydrogenatom; a C₁-C₂₀ hydrocarbon group which may be substituted; a C₁-C₂₀alkoxy group which may be substituted; a C₆-C₂₀ aryloxy group which maybe substituted; a C₆-C₂₀ alkylaryloxy group which may be substituted; aC₁-C₂₀ alkoxycarbonyl group which may be substituted; a C₆-C₂₀aryloxycarbonyl group which may be substituted; cyano group (—CN);carbamoyl group (—C(═O)NH₂); a haloformyl group (—C(═O)—X, wherein X isa halogen atom); formyl group (—C(═O)—H); and, X¹ and X², which may bethe same or different, each represents independently a leaving group).7. A process for producing a polyarylene, which comprises polymerizing ateraryl represented by formula (III) or (IV) below:

(wherein: Ar¹ and Ar², which may be the same or different, eachrepresents independently an arylene having 4 to 18 carbon atoms, whichmay be substituted and may contain 1 to 5 nitrogen atoms; R¹ and R²,which may be the same or different, each represents independently aC₁-C₂₀ hydrocarbon group which may be substituted, a C₁-C₂₀ alkoxy groupwhich may be substituted, a C₆-C₂₀aryloxy group which may besubstituted, an amine group, hydroxy group or a group shown by formula:—Si(R³)(R⁴)(R⁵) (wherein R³, R⁴ and R⁵, which may be the same ordifferent, each represents independently a C₁-C₂₀ alkyl group, a C₆-C₂₀arylalkyl group, a C₁-C₂₀ alkoxy group or a C₆-C₂₀ arylalkyloxy group);provided that, in the recurring unit of formula (III), R¹ and R² mayform together a C₄-C₂₀ saturated or unsaturated ring which may beintervened by an oxygen atom and may be substituted; A¹ and A², whichmay be the same or different, each represents independently hydrogenatom; a C₁-C₂₀ hydrocarbon group which may be substituted; a C₁-C₂₀alkoxy group which may be substituted; a C₆-C₂₀ aryloxy group which maybe substituted; a C₆-C₂₀ alkylaryloxy group which may be substituted; aC₁-C₂₀ alkoxycarbonyl group which may be substituted; a C₆-C₂₀aryloxycarbonyl group which may be substituted; cyano group (—CN);carbamoyl group (—C(═O)NH₂); a haloformyl group (—C(═O)—X, wherein X isa halogen atom); or formyl group (—C(═O)—H); and, X¹ and X², which maybe the same or different, each represents independently a leavinggroup); to produce a polyarylene represented by formula (I) or (II)below:

(wherein each of Ar¹, Ar², R¹, R², A¹ and A² has the same significanceas defined above; and n is an integer of 2 or more).
 8. A process forproducing a polyarylene, which comprises reacting ametallacyclopentadiene represented by formula (V) or (VI) below:

(wherein: Ar¹ and Ar² ₁ which may be the same or different, eachrepresents independently an arylene having 4 to 18 carbon atoms, whichmay be substituted and may contain 1 to 5 nitrogen atoms; R¹ and R²,which may be the same or different, each represents independently aC₁-C₂₀ hydrocarbon group which may be substituted, a C₁-C₂₀ alkoxy groupwhich may be substituted, a C₆-C₂₀aryloxy group which may besubstituted, an amine group, hydroxy group or a group shown by formula:—Si(R³)(R⁴)(R⁵) (wherein R³, R⁴ and R⁵, which may be the same ordifferent, each represents independently a C₁-C₂₀ alkyl group, a C₆-C₂₀arylalkyl group, a C₁-C₂₀ alkoxy group or a C₆-C₂₀ arylalkyloxy group);provided that, in the metallacyclopentadiene shown by formula (V), R¹and R² may form together a C₄-C₂₀ saturated or unsaturated ring whichmay be intervened by an oxygen atom and may be substituted; M is a metalfrom Groups III-V or the lanthanide series of the Periodic Table; L¹ andL², which may be the same or different, each represents independently ananionic ligand, provided that L¹ and L² may be crosslinked; and, X¹ andX², which may be the same or different, each represents independently aleaving group); with an alkyne derivative represented by formula (VII)below:  A^(1a)—C≡C—A^(2a)  (VII)  (wherein; A^(1a) and A^(2a), which maybe the same or different, each represents independently hydrogen atom; aC₁-C₂₀ hydrocarbon group which may be substituted; a C₁-C₂₀ alkoxy groupwhich may be substituted; a C₆-C₂₀ aryloxy group which may besubstituted; a C₆-C₂₀ alkylaryloxy group which may be substituted; aC₁-C₂₀ alkoxycarbonyl group which may be substituted; a C₆-C₂₀aryloxycarbonyl group which may be substituted; or cyano group (—CN));to produce a teraryl represented by formula (IIIa) or (IVa) below:

 (wherein each of Ar¹, Ar², R¹, R² A^(1a), A^(2a), X¹ and X² has thesame significance as defined above); and polymerizing the resultingteraryl to produce the polyarylene represented by formula (Ia) or (IIa)below:

 (wherein each of Ar¹, Ar², R², R², A^(1a) and A^(2a) has the samesignificance as defined above; and n is an integer of 2 or more).
 9. Aprocess for producing the polyarylene according to claim 8, wherein M isa metal from Group IV or the lanthanide series of the Periodic Table,and the anionic ligand is non-localized cyclic η⁵-coordination typeligand, a C₁-C₂₀ alkoxy group, a C₆-C₂₀ aryloxy group or a dialkylamidegroup.
 10. The process for producing the polyarylene according to claim9, wherein the non-localized cyclic η⁵-coordination type ligand is acyclopentadienyl, indenyl, fluorenyl or azulenyl group, which may besubstituted.
 11. The process for producing the polyarylene according toclaim 6, wherein the reaction proceeds in the presence of a compoundcontaining a metal from Groups IX-XV of the Periodic Table.
 12. Ametallacyclopentadiene represented by formula (V) or (VI) below:

(wherein: M is a metal from Groups III-V or the lanthanide series of thePeriodic Table; L¹ and L², which may be the same or different, eachrepresents independently an anionic ligand, provided that L¹ and L² maybe crosslinked; Ar¹ and Ar², which may be the same or different, eachrepresents independently an arylene having 4 to 18 carbon atoms, whichmay be substituted and may contain 1 to 5 nitrogen atoms; R¹ and R²,which may be the same or different, each represents independently aC₁-C₂₀ hydrocarbon group which may be substituted, a C₁-C₂₀ alkoxy groupwhich may be substituted, a C₆-C₂₀ aryloxy group which may besubstituted, an amine group, hydroxy group or a group shown by formula:—Si(R³)(R⁴)(R⁵)(wherein R³, R⁴ and R⁵, which may be the same ordifferent, each represents independently a C₁-C₂₀ alkyl group, a C₆-C₂₀arylalkyl group, a C₁-C₂₀ alkoxy group or a C₆-C₂₀ arylalkyloxy group);provided that, in the metallacyclopentadiene shown by formula (V), R¹and R² may form together a C₄-C₂₀ saturated or unsaturated ring whichmay be intervened by an oxygen atom and may be substituted; and, X¹ andX², which may be the same or different, each represents independently aleaving group).
 13. A polyarylene comprising a recurring unitrepresented by formula (I) below:

(wherein: Ar¹ and Ar², which may be the same or different, eachrepresents independently a paraarylene having 4 to 18 carbon atoms,which may be substituted and may contain 1 to 5 nitrogen atoms; R¹ andR², which may be the same or different, each represents independently aC₁-C₂₀ hydrocarbon group which may be substituted, a C₁-C₂₀ alkoxy groupwhich may be substituted, a C₆-C₂₀aryloxy group which may besubstituted, an amine group, hydroxy group or a group shown by formula:—Si(R³)(R⁴)(R⁵) (wherein R³, R⁴ and R⁵, which may be the same ordifferent, each represents independently a C₁-C₂₀ alkyl group, a C₆-C₂₀arylalkyl group, a C₁-C₂₀ alkoxy group or a C₆-C₂₀ arylalkyloxy group);provided that, in the recurring unit of formula (I), R¹ and R² may formtogether a C₄-C₂₀ saturated or unsaturated ring which may be intervenedby an oxygen atom and may be substituted; A¹ and A², which may be thesame or different, each represents independently hydrogen atom; a C₁-C₂₀hydrocarbon group which may be substituted; a C₁-C₂₀ alkoxy group whichmay be substituted; a C₆-C₂₀ aryloxy group which may be substituted; aC₆-C₂₀ alkylaryloxy group which may be substituted; an alkoxycarbonylgroup which may be substituted; a C₆-C₂₀ aryloxycarbonyl group which maybe substituted; cyano group (—CN); carbamoyl group (—C(═O)NH₂); ahaloformyl group (—C(═O)—X, wherein X is a halogen atom); or formylgroup (—C(═O)—H); and, n is an integer of 2 or more).
 14. Thepolyarylene according to claim 13, wherein each of Ar¹ and Ar², whichmay be the same or different, represents independently a paraphenylenegroup which may be substituted.
 15. The polyarylene according to claim13, which has the recurring unit shown by formula (I) above, wherein R¹and R² form together a C₄-C₂₀ saturated or unsaturated ring which may beintervened by an oxygen atom and may be substituted.
 16. The polyaryleneaccording to claim 13, wherein the C₁-C₂₀ hydrocarbon group is a linearor branched C₁-C₂₀ alkyl group, a linear or branched C₂-C₂₀ alkenylgroup, a linear or branched C₂ -C₂₀ alkynyl group, a linear or branchedC₃-C₂₀ allyl group, a linear or branched C₄ -C₂₀ alkadienyl group, alinear or branched C₄-C₂₀ polyenyl group, a C₆-C₁₈ aryl group, a C₆-C₂₀alkylaryl group, a C₆-C₂₀ arylalkyl group, a C₄-C₂₀ cycloalkyl group, ora C₄-C₂₀ cycloalkenyl group.
 17. A resin composition comprising thepolyarylene according to claim 13 and a synthetic organic polymer. 18.The process for producing the polyarylene according to claim 7, whereinthe reaction proceeds in the presence of a compound containing a metalfrom Groups IX-XV of the Periodic Table.
 19. The process for producingthe polyarylene according to claim 8, wherein the reaction proceeds inthe presence of a compound containing a metal from Groups IX-XV of thePeriodic Table.